Chiral 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives, processes for their preparation and their use as herbicides and plant growth regulators

ABSTRACT

The present invention provides chiral 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives of the formula (I) and their salts 
                         
processes for their preparation and their use as herbicides and plant growth regulators, in particular as herbicides for the selective control of harmful plants in crops of useful plants.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a §371 national stage application of PCT/EP2008/009437 filed Nov. 8, 2008, which claims priority to European Application EP 07023198.0 filed Nov. 30, 2007.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives. The present invention furthermore provides mixtures of the thiazole derivatives mentioned above with other herbicides and/or safeners. In addition, the present invention relates to processes for preparing the thiazole derivatives mentioned above and to the use of these compounds as plant growth regulators alone and in combination with safeners and/or in mixtures with other herbicides, in particular to their use for controlling plants in specific crop plants or as crop protection regulators.

2. Description of Related Art

It is already known from the prior art that certain 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives have herbicidal properties. Thus the Japanese patent application JP 2003/096059 describes herbicidally active thiazole derivatives which carry a benzylthio or benzylsulfonyl group as substituents at the 2-position of the thiazole ring.

WO 2006/123088 describes various 2-[(pyrazolylmethyl)thio]-, 2-[(pyrazolylmethyl)sulfinyl]- and 2-[(pyrazolylmethyl)sulfonyl]thiazole derivatives, their preparation and their use as herbicides.

However, on application, the active compounds already known from the publications mentioned above have disadvantages, be it

-   (a) that they have no or else insufficient herbicidal activity     against harmful plants, -   (b) that the spectrum of harmful plants that can be controlled with     an active compound is not wide enough, or -   (c) that their selectivity in crops of useful plants is     insufficient.

In particular, the herbicidally active thiazole compounds known from the prior art have unsatisfactory herbicidal activity against certain weed grasses and at the same time unsatisfactory crop plant compatibility in certain crops.

SUMMARY OF THE INVENTION

It is therefore desirable to provide alternative chemical active compounds based on thiazole derivatives which can be used as herbicides or plant growth regulators and which are associated with certain advantages compared to systems known from the prior art.

It is thus the general object of the present invention to provide alternative thiazole derivatives which can be used as herbicides or plant growth regulators, in particular those having a satisfactory herbicidal action against harmful plants, covering a broad spectrum of harmful plants and/or having high selectivity in crops of useful plants. Preferably, these thiazole derivatives should have a better property profile, in particular better herbicidal activity against harmful plants, cover a broader spectrum of harmful plants and/or have higher selectivity in crops of useful plants than the thiazole derivatives known from the prior art.

A particular object of the present invention is to provide herbicidally active thiazole compounds having improved herbicidal activity against weed grasses compared to thiazole derivatives known from the prior art.

Another particular object of the present invention is to provide herbicidally active thiazole compounds having improved compatibility in specific crops compared to thiazole derivatives known from the prior art.

A particular object of the present invention is to provide herbicidally active thiazole compounds which, at the same time, have improved herbicidal activity against certain weed grasses and improved compatibility in specific crops compared to thiazole derivatives known from the prior art.

The present invention now provides specific 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives optically active at the sulfoxide function, which compounds have advantages compared to the compounds known from the prior art or racemic mixtures thereof.

According to the invention, it has been found that these inventive 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives optically active at the sulfoxide function have improved herbicidal activity against certain weed grasses compared to thiazole derivatives known from the prior art.

According to the invention, it has furthermore been found that these inventive 2-(benzylsulfinyl)thiazole derivatives and 2-[(1H-pyrazol-4-ylmethyl)sulfinyl]thiazole derivatives optically active at the sulfoxide function have improved crop plant compatibility in specific crops compared to thiazole derivatives known from the prior art.

Accordingly, the present invention provides optically active compounds of the formula (I), their agrochemically acceptable salts and their agrochemically acceptable quaternized nitrogen derivatives

in which

-   Y is either

and

-   -   the substituents R¹ to R⁸ are each independently of one another         selected from the group consisting of         -   hydrogen, halogen, hydroxyl, cyano, nitro, amino, C(O)OH,             formyl,         -   (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkylcarbonyl,             (C₁-C₆)-haloalkylcarbonyl, (C₁-C₆)-alkylcarbonyloxy,             (C₁-C₆)-haloalkylcarbonyloxy,             (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-alkyl,             (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-alkyl,             (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-haloalkyl,             (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-haloalkyl,         -   (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₁-C₆)-alkoxycarbonyl,             (C₁-C₆)-haloalkoxycarbonyl,             (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkyl,             (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-alkyl,             (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-haloalkyl,             (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-haloalkyl,         -   (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl,             (C₂-C₆)-alkenylcarbonyl, (C₂-C₆)-haloalkenylcarbonyl,             (C₂-C₆)-alkenyloxy, (C₂-C₆)-haloalkenyloxy,             (C₂-C₆)-alkenyloxycarbonyl, (C₂-C₆)-haloalkenyloxycarbonyl,         -   (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl,             (C₂-C₆)-alkynylcarbonyl, (C₂-C₆)-haloalkynylcarbonyl,             (C₂-C₆)-alkynyloxy, (C₂-C₆)-haloalkynyloxy,             (C₂-C₆)-alkynyloxycarbonyl, (C₂-C₆)-haloalkynyloxycarbonyl,         -   (C₁-C₆)-alkylthiocarbonyl, (C₁-C₆)-haloalkylthiocarbonyl,             (C₁-C₆)-alkylthiocarbonyloxy,             (C₁-C₆)-haloalkylthiocarbonyloxy,         -   (C₁-C₆)-alkylthio-(C₁-C₆)-alkoxy,             (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyl,             (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyloxy,         -   (C₆-C₁₄)-aryl, (C₆-C₁₄)-aryloxy, (C₆-C₁₄)-arylcarbonyl,             (C₆-C₁₄)-aryloxycarbonyl,         -   (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxy,             (C₆-C₁₄)-aryloxy-(C₁-C₆)-alkyl,             (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl-carbonyl,             (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl-carbonyloxy,             (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyl,             (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyloxy,         -   (C₁-C₆)-alkylsulfonyl, (C₁-C₆)-alkylthio,             (C₁-C₆)-alkylsulfinyl, (C₁-C₆)-haloalkylsulfonyl,             (C₁-C₆)-haloalkylthio, (C₁-C₆)-haloalkylsulfinyl,             (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-alkyl,             (C₁-C₆)-alkylthio-(C₁-C₆)-alkyl,             (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-alkyl,             (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-alkyl,             (C₁-C₆)-haloalkylthio-(C₁-C₆)-alkyl,             (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-alkyl,             (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-haloalkyl,             (C₁-C₆)-alkylthio-(C₁-C₆)-haloalkyl,             (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-haloalkyl,             (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-haloalkyl,             (C₁-C₆)-haloalkylthio-(C₁-C₆)-haloalkyl,             (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-haloalkyl,             (C₁-C₆)-alkylsulfonyloxy, (C₁-C₆)-haloalkylsulfonyloxy,         -   (C₄-C₁₄)-arylsulfonyl, (C₆-C₁₄)-arylthio,             (C₆-C₁₄)-arylsulfinyl,         -   mono-((C₁-C₆)-alkyl)-amino, mono-((C₁-C₆)-haloalkyl)-amino,             di-((C₁-C₆)-alkyl)-amino, di-((C₁-C₆)-haloalkyl)-amino,             ((C₁-C₆)-alkyl-(C₁-C₆)-haloalkyl)-amino,             N-((C₁-C₆)-alkanoyl)-amino, N-((C₁-C₆)-haloalkanoyl)-amino,             aminocarbonyl-(C₁-C₆)-alkyl,             mono-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl,             di-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl,             mono-((C₁-C₆)-alkyl)-aminocarbonyl,         -   (C₁-C₆)-alkoxy-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkoxy,             (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkoxy,         -   (C₃-C₈)-cycloalkyl, (C₃-C₈)-cycloalkoxy,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkyl,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkyl,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxy,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxy,             (C₃-C₈)-cycloalkylcarbonyl, (C₃-C₈)-cycloalkoxycarbonyl,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyl,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyl,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyl,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyl,             (C₃-C₈)-cycloalkylcarbonyloxy,             (C₃-C₈)-cycloalkoxycarbonyloxy,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyloxy,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyloxy,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyloxy,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyloxy,         -   (C₃-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkenyloxy,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkyl,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkyl,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxy,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxy,             (C₃-C₈)-cycloalkenylcarbonyl,             (C₃-C₈)-cycloalkenyloxycarbonyl,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyl,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyl,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyl,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyl,             (C₃-C₈)-cycloalkenylcarbonyloxy,             (C₃-C₈)-cycloalkenyloxycarbonyloxy,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyloxy,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyloxy,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyloxy,             (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyloxy,         -   (C₃-C₈)-cycloalkylthio, (C₃-C₈)-alkenylthio,             (C₃-C₈)-cycloalkenylthio, (C₃-C₆)-alkynylthio,         -   hydroxy-(C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkoxy,             cyano-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkyl,         -   3-oxetanyloxy,         -   C(O)NR⁹R¹⁰ where R⁹ and R¹⁰ independently of one another are             hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,             (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a             (C₁-C₆)-alkylene group which may contain one oxygen or             sulfur atom or one or two amino or (C₁-C₆)-alkylamino             groups, where the radicals mentioned may, if appropriate, be             attached cyclically to one another, provided they are ortho             to one another             -   and/or             -   two substituents ortho to one another together form a                 (C₁-C₆)-alkylene group which may contain one or more                 oxygen and/or sulfur atoms, where the (C₁-C₆)-alkylene                 group may be mono- or polysubstituted by halogen and the                 halogen substituents in question may be identical or                 different; and     -   the substituents R¹¹ and R¹², in each case independently of one         another, are selected from the group consisting of         -   hydrogen, halogen, nitro, cyano, formyl, C(O)OH, hydroxyl,             amino,         -   (C₁-C₆)-alkyl, (C₁-C₆)-alkylcarbonyl,             (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-alkyl,             (C₁-C₆)-alkylcarbonyloxy,         -   (C₁-C₆)-alkoxy, (C₁-C₆)-alkoxycarbonyl,             (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkyl,             (C₁-C₆)-alkoxy-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkoxy,             (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkoxy,         -   (C₂-C₆)-alkenyl, (C₂-C₆)-alkenyloxy, (C₂-C₆)-alkynyl,             (C₂-C₆)-alkynyloxy,         -   (C₁-C₆)-alkylthio, (C₁-C₆)-alkylsulfinyl,             (C₁-C₆)-alkylsulfonyl, (C₁-C₆)-alkylsulfonyloxy,             (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-alkyl,             (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-alkyl,             (C₁-C₆)-alkylthio-(C₁-C₆)-alkyl,             (C₁-C₆)-alkylthio-(C₁-C₆)-alkoxy,         -   mono-((C₁-C₆)-alkyl)-amino, di-((C₁-C₆)-alkyl)-amino,             N-((C₁-C₆)-alkanoyl)-amino, aminocarbonyl-(C₁-C₆)-alkyl,             mono-((C₁-C₆)-alkyl)-aminocarbonyl,             di-((C₁-C₆)-alkyl)-aminocarbonyl,             mono-((C₁-C₆)-alkyl)-aminosulfonyl,             di-((C₁-C₆)-alkyl)-aminosulfonyl,         -   (C₃-C₈)-cycloalkyl, (C₃-C₈)-cycloalkoxy,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkyl,             (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxy,             (C₃-C₈)-cycloalkylcarbonyl, (C₃-C₈)-cycloalkoxycarbonyl,         -   (C₃-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkenyloxy,             (C₃-C₈)-cycloalkylthio, (C₃-C₈)-cycloalkylsulfinyl,             (C₃-C₈)-cycloalkylsulfonyl, (C₃-C₈)-cycloalkylsulfonyloxy,         -   cyano-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkyl,         -   (C₆-C₁₄)-aryl, (C₆-C₁₄)-aryloxy,             (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxy,             (C₆-C₁₄)-aryloxy-(C₁-C₆)-alkyl,         -   CONH—SO₂—(C₁-C₆)-alkyl, —NHCHO, —NHCO—(C₁-C₆)-alkyl,             —NHCO₂—(C₁-C₆)-alkyl, —NHCONH—(C₁-C₆)-alkyl,             —NHSO₂—(C₁-C₆)-alkyl, —OCONH—(C₁-C₆)-alkyl,             (C₁-C₆)-alkylaminosulfonyl-(C₁-C₂)-alkyl,             di-(C₁-C₆)-alkylaminosulfonyl-(C₁-C₂)-alkyl, —C(O)NHR⁹,             —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another             are hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,             (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a             (C₁-C₆)-alkylene group which may contain one oxygen or             sulfur atom or one or two amino or (C₁-C₆)-alkylamino             groups,     -   where the radicals R¹¹ and R¹² mentioned above may be mono-or         polysubstituted independently of one another by radicals         selected from the group consisting of halogen and (C₁-C₆)-alkyl;         and     -   where the radicals cycloalkyl and aryl may be mono- or         polysubstituted independently of one another.

If the radicals comprising cycloalkyl and aryl are substituted, the substituents are preferably selected from the group consisting of (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkoxy, nitro, cyano, (C₁-C₃)-cycloalkyl, (C₁-C₆)-haloalkoxy, (C₁-C₆)-alkylthio, (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-alkoxycarbonyl and halogen, where the radicals mentioned may, if appropriate, be cyclically attached to one another, provided they are ortho to each other.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

A first embodiment of the present invention comprises compounds of the formula (I) in which

-   Y is

and

-   R¹ is preferably selected from the group consisting of hydrogen,     hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy,     (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,     (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl,     (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino,     C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl,     (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl,     C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,     phenyl, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another     are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together     form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur     atom or one or two amino or (C₁-C₆)-alkylamino groups; -   R¹ is particularly preferably selected from the group consisting of     H, F, Cl, Br, I, CN, OH, NH₂, NO₂, Me, Et, Ph, CHF₂, CF₃, OMe, OEt,     OPr, OiPr, OBu, OcPen, OcHex, OCHF₂, OCF₃, OCH₂CF₃, C(O)OH, C(O)OMe,     C(O)OEt, C(O)OPr, C(O)OiPr, C(O)OBu, C(O)OiBu, C(O)OsBu, C(O)OcPen,     C(O)OCH₂CH═CH₂, C(O)OCH₂C≡CH, C(O)OCH₂Ph, CH₂OMe, CH₂OEt, CH₂OBu,     OCH₂cPr, OCH₂CH═CH₂, OCH₂C≡CH, OCH₂Ph, OCH₂C(O)OMe, OCH₂C(O)OEt,     OCH₂CH₂C(O)OMe, OCH₂CH₂C(O)OEt, OC(O)Me, OSO₂Me, S(O)Me, SCF₃,     S(O)CF₃ and S(O)₂CF₃; -   R¹ is very particularly preferably selected from the group     consisting of H, F, Cl, Br, Me, CHF₂, CF₃, OMe, OCHF₂, OCF₃,     OCH₂CF₃, I and OEt.

A second embodiment of the present invention comprises compounds of the formula (I) in which

-   Y is

and

-   R² is preferably selected from the group consisting of hydrogen,     hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy,     (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,     (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl,     (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino,     C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl,     (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl,     C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,     phenyl, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another     are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together     form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur     atom or one or two amino or (C₁-C₆)-alkylamino groups; -   R² is particularly preferably selected from the group consisting of     H, F, Cl, Br, OH, NO₂, Me, iPr, CHF₂, CF₃, OMe, OEt, OPr, OiPr, OBu,     OCHF₂, OCF₃, OCH₂CF₃, C(O)OH and C(O)OMe; -   R² is very particularly preferably selected from the group     consisting of H, F, Cl, Me, CF₃ and OMe.

A third embodiment of the present invention comprises compounds of the formula (I) in which

-   Y is

and

-   R³ is preferably selected from the group consisting of hydrogen,     hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy,     (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,     (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl,     (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino,     C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl,     (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl,     C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,     phenyl, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another     are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together     form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur     atom or one or two amino or (C₁-C₆)-alkylamino groups; -   R³ is particularly preferably selected from the group consisting of     H, F, Cl, Br, OH, Me, CF₃, OMe, OCHF₂, OCF₃, OCH₂CF₃, C(O)OMe and     C(O)OEt; and -   R³ is very particularly preferably selected from the group     consisting of H, F, Cl, Br, CF₃ and Me.

A fourth embodiment of the present invention comprises compounds of the formula (I) in which

-   Y is

and

-   R⁴ is preferably selected from the group consisting of hydrogen,     hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy,     (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,     (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl,     (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino,     C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl,     (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl,     C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,     phenyl, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another     are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together     form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur     atom or one or two amino or (C₁-C₆)-alkylamino groups; -   R⁴ is particularly preferably selected from the group consisting of     H, F, Cl, Br, NO₂, Me, iPr, OMe, OEt, OPr, OiPr, OBu, OCHF₂, CF₃,     OCF₃, OCH₂CF₃, OCH₂CH═CH₂ and OCH₂C≡CH; and -   R⁴ is very particularly preferably selected from the group     consisting of H, F, Cl, Me, CF₃ and OMe.

A fifth embodiment of the present invention comprises compounds of the formula (I) in which

-   Y is

and

-   R⁵ is preferably selected from the group consisting of hydrogen,     hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy,     (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio,     (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl,     (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino,     C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl,     (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl,     C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl,     phenyl, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another     are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together     form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur     atom or one or two amino or (C₁-C₆)-alkylamino groups; -   R⁵ is particularly preferably selected from the group consisting of     H, F, Cl, Br, OH, NO₂, NMe₂, NEt₂, Me, Et, CHF₂, CF₃, OMe, OEt, OPr,     OiPr, OBu, OiBu, OCHF₂, OCF₃, OCH₂CF₃, C(O)OH, C(O)OMe, C(O)OEt,     C(O)OPr, C(O)OiPr, C(O)OBu, C(O)OiBu, C(O)OsBu, C(O)OCH₂Ph,     OCH₂CH═CH₂ and OCH₂C≡CH; and -   R⁵ is very particularly preferably selected from the group     consisting of H, F, Cl, Me, CF₃, OCHF₂, OCF₃ and OMe.

In the context of the first to fifth embodiment of the present invention, it is possible to combine the specific preferred, particularly preferred and very particularly preferred meanings of the substituents R¹ to R⁵ as desired. This means that the present invention comprises compounds of the formula (I) where Y is

in which, for example, the substituent R¹ has a preferred meaning and the substituents R² to R⁵ have the general meaning, or else, for example, the substituent R² has a preferred meaning, the substituent R³ has a particularly preferred meaning, the substituent R⁴ has a very particular meaning and the substituents R¹ and R⁵ have the general meaning.

A sixth embodiment of the present invention comprises compounds of the formula (I) in which

-   Y is

and

-   R⁶ is preferably selected from the group consisting of hydrogen,     halogen, hydroxyl, cyano, nitro, amino, (C₁-C₄)-alkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₃-C₆)-cycloalkoxy,     (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio,     (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, di-(C₁-C₄)-alkylamino,     (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₃-C₄)-alkenyloxy,     (C₃-C₄)-alkynyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy,     hydroxy-(C₁-C₂)-alkyl, hydroxy-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkoxy,     cyano-(C₁-C₂)-alkyl, phenyl, phenyl-(C₁-C₂)-alkyl,     phenyl-(C₁-C₂)-alkoxy, phenoxy, (C₁-C₄)-alkylcarbonyloxy,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylcarbonyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl     and 3-oxetanyloxy, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of     one another are selected from the group consisting of hydrogen,     (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹     and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain one     oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino     groups; and -   R⁶ is particularly preferably selected from the group consisting of     H, F, Cl, Br, I, CN, Me, Et, Pr, iPr, tBu, CHF₂, CF₃, OMe, OEt,     OCHF₂ and OCH₂CF₃; and -   R⁶ is very particularly preferably selected from the group     consisting of F, Cl, Br, CHF₂, CF₃, OCHF₂, OCF₃, OCH₂CF₃, Me, OMe     and Et.

A seventh embodiment of the present invention comprises compounds of the formula (I) in which

-   Y is

and

-   R⁷ is preferably selected from the group consisting of hydrogen,     (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, phenyl, phenyl-(C₁-C₂)-alkyl,     (C₃-C₆)-cycloalkyl; (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl, where the     cycloalkyl radical is optionally substituted by (C₁-C₄)-alkyl;     (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, cyano-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl,     mono-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₂)-alkyl,     di-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₂)-alkyl, hydroxy-(C₁-C₄)-alkyl,     (C₁-C₄)-alkylcarbonyl-(C₁-C₄)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl;     phenylsulfonyl which is optionally substituted by one or more     identical or different radicals from the group consisting of     halogen, nitro, cyano, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl,     (C₃-C₆)-cycloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and     (C₁-C₆)-alkylthio; (C₁-C₄)-alkylcarbonyl; phenylcarbonyl which is     optionally substituted by one or more identical or different     radicals from the group consisting of halogen, nitro, cyano,     (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₆)-cycloalkyl,     (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy and (C₁-C₆)-alkylthio; and     (C₁-C₄)-alkoxycarbonyl; -   R⁷ is particularly preferably selected from the group consisting of     H, Me, Et, Pr, cPr, iPr, Bu, iBu, sBu, tBu, cPen, cHex, CHF₂,     CH₂CF₃, Ph, Ph(4-Cl), CH₂cPr, CH₂cPr(2-Me), CHMecPr, CH₂cBu,     CH₂cPen, CH₂cHex, CH₂Ph, CH₂CH═CH₂, CH₂C≡CH, CHMeC≡CH, CH₂C≡CMe,     CH₂OMe, CH₂OEt, CH₂CH₂OH, CH₂CH₂OMe, CH₂CH₂OEt, CH₂CH₂C(O)Me,     CH₂SMe, CH₂SO₂Me, CH₂CN, CH₂C(O)OMe, CH₂C(O)OEt, CH₂C(O)NH₂,     CH₂C(O)NMe₂, CH₂C(O)Me, SO₂Me, SO₂Ph, C(O)Me, C(O)Ph and C(O)OMe;     and -   R⁷ is very particularly preferably selected from the group     consisting of Me, Et and CHF₂.

An eighth embodiment of the present invention comprises compounds of the formula (I) in which

-   Y is

and

-   R⁸ is preferably selected from the group consisting of hydrogen,     halogen, hydroxyl, cyano, nitro, amino, (C₁-C₄)-alkyl,     (C₁-C₄)-haloalkyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl,     (C₃-C₆)-cycloalkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio,     (C₁-C₄)-alkylthio-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfinyl-(C₁-C₂)-alkyl, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkylsulfonyl-(C₁-C₂)-alkyl, di-(C₁-C₄)-alkylamino,     (C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl, cyano-(C₁-C₄)-alkyl,     (C₂-C₄)-alkynyl, (C₃-C₄)-alkenyloxy, (C₃-C₄)-alkynyloxy,     (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, hydroxy-(C₁-C₂)-alkyl,     hydroxy-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkoxy, cyano-(C₁-C₂)-alkyl,     phenyl, phenyl-(C₁-C₂)-alkyl, phenyl-(C₁-C₂)-alkoxy, phenoxy,     (C₁-C₄)-alkylcarbonyloxy, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkylcarbonyl-(C₁-C₂)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkyl, aminocarbonyl-(C₁-C₂)-alkyl     and 3-oxetanyloxy, —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of     one another are selected from the group consisting of hydrogen,     (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹     and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain one     oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino     groups; and -   R⁸ is particularly preferably selected from the group consisting of     H, F, Cl, Br, I, CN, Me, Et, CHF₂, CF₃, OCHF₂, OCH₂CF₃, OMe, OEt,     OPr, OiPr, OtBu, SO₂Me, SO₂iPr, 3-Oxetanyloxy-, OPh, OCH₂CH═CH₂,     OCH₂C≡CH, OCH₂CHF₂, SEt, OCH₂CH₂OCH₃, SMe, OCH₂CH₂CH₂F, OCH(CH₂F)₂,     OCH₂CF═CH₂, OCH(CH₃)CF₃, OCH₂CN, OCH(CH₃)CH₂F, OCH₂CF₂CHF₂ and     OCH(CH₃)₂; and -   R⁸ is very particularly preferably selected from the group     consisting of F, Cl, Br, CHF₂, CF₃, OCHF₂ and OCH₂CF₃.

In the context of the sixth to eighth embodiments of the present invention, it is possible to combine the individual preferred, particularly preferred and very particularly preferred meanings of the substituents R⁶ to R⁸. This means that the present invention comprises compounds of the formula (I) where Y is

in which, for example, the substituent R⁶ has a preferred meaning and the substituents R⁷ and R⁸ have the general meaning, or else the substituent R⁷ has a preferred meaning, the substituent R⁸ has a particularly preferred meaning and the substituent R⁶ has a very particularly preferred meaning.

The preferred, particularly preferred and very particularly preferred definitions of the radicals R¹ to R⁸ defined in these embodiments of the present invention can be combined in any combination with the meanings of the substituents R¹¹ and R¹² defined hereinbelow as preferred.

Accordingly, preferred, particularly preferred and very particularly preferred meanings of the radicals R are as follows:

Preferred meanings of the radicals R¹¹ and R¹² can be selected independently of one another from the group consisting of

-   -   H, halogen, nitro, cyano, carboxyl, (C₁-C₆)-alkyl,         (C₃-C₆)-cycloalkyl, (C₃-C₆)-cycloalkoxy, (C₁-C₆)-alkoxy,         (C₁-C₆)-alkylcarbonyl, (C₃-C₆)-cycloalkylcarbonyl,         (C₁-C₆)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl,         mono-((C₁-C₄)-alkyl)-aminocarbonyl,         di-((C₁-C₄)-alkyl)-aminocarbonyl,         mono-((C₁-C₄)-alkyl)-aminosulfonyl,         di-((C₁-C₄)-alkyl)-aminosulfonyl, (C₁-C₄)-alkylthio,         (C₃-C₆)-cycloalkylthio, (C₁-C₄)-alkylsulfinyl,         (C₃-C₆)-cycloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl,         (C₃-C₆)-cycloalkylsulfonyl, (C₁-C₄)-alkylsulfonyloxy,         (C₃-C₆)-cycloalkylsulfonyloxy, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl,         (C₂-C₃)-alkenyloxy, (C₂-C₃)-alkynyloxy, —NHCO—(C₁-C₃)-alkyl,         —NHCO₂—(C₁-C₃)-alkyl, —NHCONH—(C₁-C₃)-alkyl,         —NHSO₂—(C₁-C₃)-alkyl, —OCONH—(C₁-C₃)-alkyl, —CONHR⁹, —CONR⁹R¹⁰,         -   where R⁹ and R¹⁰ independently of one another are hydrogen,             (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl,         -   where the radicals R¹¹ and R¹² mentioned above may be mono-             or polysubstituted independently of one another by radicals             selected from the group consisting of halogen and             (C₁-C₆)-alkyl.

Particularly preferred meanings of the radicals R¹¹ and R¹² can be selected independently of one another from the group consisting of H, F, Cl, Br, I, Me, Et, NO₂, C(O)OEt, CHF₂ and CF₃.

Very particularly preferred meanings of the radicals R¹¹ and R¹² can be selected independently of one another from the group consisting of H, F, Cl, Br, I, Me, CHF₂, NO₂ and CF₃, with F, Cl, Br and I being most preferred.

In the context of the present invention, the compounds of the formula (I) also comprise compounds quaternized at a nitrogen atom by a) protonation, b) alkylation or c) oxidation.

In addition, the present invention also provides compounds of the formula (Ic) in racemic form

in which Y corresponds to

and the radicals R¹ to R⁵ and R¹¹ and R¹² have the above general, preferred, particularly preferred and very particularly preferred meanings, except for the compound 2-benzylsulfinylthiazole and the compounds 2-(benzylsulfinyl)-1,3-thiazole, 2-(benzylsulfinyl)-5-(chloromethyl)-1,3-thiazole, 5-(chloromethyl)-2-[(4-methylbenzyl)sulfinyl]-1,3-thiazole, 5-(chloromethyl)-2-[(4-methoxybenzyl)sulfinyl]-1,3-thiazole, 2-[(4-chlorobenzyl)sulfinyl]-5-(chloromethyl)-1,3-thiazole, 5-(chloromethyl)-2-[(4-nitrobenzyl)sulfinyl]-1,3-thiazole, 5-(bromomethyl)-2-[(4-nitrobenzyl)sulfinyl]-1,3-thiazole, 5-(bromomethyl)-2-[(4-chlorobenzyl)sulfinyl]-1,3-thiazole, 5-(bromomethyl)-2-[(4-methoxybenzyl)sulfinyl]-1,3-thiazole, 5-(bromomethyl)-2-[(4-methylbenzyl)sulfinyl]-1,3-thiazole, 2-(benzylsulfinyl)-5-(bromomethyl)-1,3-thiazole.

Except for the compound 2-benzylsulfinylthiazole (J. Heterocyclic Chem. 1978, 15(8), 1361), corresponding compounds of the formula (Ic) are not known. J. Heterocyclic Chem. 1978, 15(8), 1361 does not disclose any information as to the herbicidal action of corresponding compounds.

If appropriate, the compounds of the formula (I) may be able to form salts by forming an adduct with a suitable inorganic or organic acid, such as, for example, HCl, HBr, H₂SO₄ or HNO₃, or else oxalic acid or sulfonic acids, to a basic group, such as, for example, amino or alkylamino. Suitable substituents present in deprotonated form, such as, for example, sulfonic acids or carboxylic acids, are capable of forming inner salts with groups, such as amino groups, which for their part can be protonated. Salts can also be formed by replacing the hydrogen of suitable substituents, such as, for example, sulfonic acids or carboxylic acids, with a cation suitable in the agrochemical sector. These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, especially sodium salts or potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts having cations of the formula [NRR′R″R′″]⁺ in which R to R′″ in each case independently denote an organic radical, in particular alkyl, aryl, aralkyl or alkylaryl.

In the formula (I) and in all the other formulae of the present invention, the radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl and haloalkylsulfonyl and the corresponding unsaturated and/or substituted radicals can in each case be straight-chain or branched in the carbon skeleton. Unless indicated specifically, preference is given for these radicals to the lower carbon skeletons, for example those having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms, or in the case of unsaturated groups having 2 to 6 carbon atoms, especially 2 to 4 carbon atoms. Alkyl radicals, also in composite definitions such as alkoxy, haloalkyl, etc., are for example methyl, ethyl, propyls, such as n-propyl or isopropyl, butyls, such as n-butyl, isobutyl or tert-butyl, pentyls, such as n-pentyl, isopentyl or neopentyl, hexyls, such as n-hexyl, isohexyl, 3-methylpentyl, 2,2-dimethylbutyl or 2,3-dimethylbutyl, heptyls, such as n-heptyl, 1-methylhexyl or 1,4-dimethylpentyl; alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals; where at least one double bond or triple bond is present, preferably one double bond or triple bond, respectively. Alkenyl is, for example, vinyl, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl, and 1-methylbut-2-en-1-yl; alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, but-3-yn-1-yl and 1-methylbut-3-yn-1-yl.

Cycloalkyl groups are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. The cycloalkyl groups can be present in bi- or tricyclic form.

If haloalkyl groups and haloalkyl radicals of haloalkoxy, haloalkylthio, haloalkenyl, haloalkynyl etc. are stated, the lower carbon skeletons of these radicals having, for example, 1 to 6 carbon atoms or 2 to 6 carbon atoms, in particular 1 to 4 carbon atoms or preferably 2 to 4 carbon atoms, and the corresponding unsaturated and/or substituted radicals are in each case straight-chain or branched in the carbon skeleton. Examples are difluoromethyl, 2,2,2-trifluoroethyl, trifluoroallyl, 1-chloroprop-1-yl-3-yl. According to the invention, the term “halo” is used synonymously with “halogen”.

Alkylene groups in these radicals are the lower carbon skeletons, for example those having 1 to 10 carbon atoms, in particular 1 to 6 carbon atoms, or preferably 2 to 4 carbon atoms (unless defined otherwise), and also the corresponding unsaturated and/or substituted radicals in the carbon skeleton which may in each case be straight-chain or branched. Examples are methylene, ethylene, n- and isopropylene and n-, s-, iso-, t-butylene.

Hydroxyalkyl groups in these radicals are the lower carbon skeletons, for example those having 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms, and also the corresponding unsaturated and/or substituted radicals in the carbon skeleton which may in each case be straight-chain or branched. Examples of these are 1,2-dihydroxyethyl and 3-hydroxypropyl.

Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl, haloalkenyl and haloalkynyl are alkyl, alkenyl or alkynyl, respectively, which are fully or partly substituted by halogen, preferably by fluorine, chlorine or bromine, in particular by fluorine and/or chlorine, examples being monohaloalkyl (i.e., monohalogenalkyl), perhaloalkyl, CF₃, CHF₂, CH₂F, CF₃CF₂, CH₂FCHCl, CCl₃, CHCl₂, CH₂CH₂Cl; haloalkoxy is, for example, OCF₃, OCHF₂, OCH₂F, CF₃CF₂O, OCH₂CF₃ and OCH₂CH₂Cl; this correspondingly applies to haloalkenyl and other halogen-substituted radicals.

Aryl is a monocyclic, bicyclic or polycyclic aromatic system, for example phenyl or naphthyl, preferably phenyl.

The definition “substituted by one or more radicals” refers, unless otherwise defined, to one or more identical or different radicals.

The substituents given by way of example (“first substituent level”) can, if they include hydrocarbon-containing fractions, be further substituted therein if desired (“second substituent level”), by for example one of the substituents as defined for the first substituent level. Corresponding further substituent levels are possible. The term “substituted radical” preferably embraces just one or two substituent levels.

In the case of radicals having carbon atoms, preference is given to those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms. Preference is generally given to substituents from the group consisting of halogen, for example fluorine and chlorine, (C₁-C₄)-alkyl, preferably methyl or ethyl, (C₁-C₄)-haloalkyl, preferably trifluoromethyl, (C₁-C₄)-alkoxy, preferably methoxy or ethoxy, (C₁-C₄)-haloalkoxy, nitro and cyano.

If an aryl radical is substituted, it may preferably be phenyl which is mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group consisting of halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy, cyano and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-trifluoromethyl and 2-, 3- and 4-trichloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

Primarily for reasons of higher herbicidal activity, better selectivity and/or better producibility, compounds of the formula (I) according to the invention or their agrochemical salts or quaternary N derivatives are of particular interest in which individual radicals have one of the preferred meanings already specified or specified below, or in particular those in which one or more of the preferred meanings already specified or specified below occur in combination.

The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials and the intermediates required in each case for the preparation. These radical definitions can be exchanged for one another as desired, i.e. including combinations between the given preferred ranges.

The present compounds of the formula (I) have a chiral sulfur atom which, in the structure shown above, is illustrated by the marker (*). According to the rules of Cahn, Ingold and Prelog (CIP rules), this sulfur atom can have either an (R) configuration or an (S) configuration.

The present invention encompasses compounds of the formula (I) both with (S) and with (R) configuration, i.e. the present invention encompasses the compounds of the formula (I) in which the sulfur atom in question has

-   (1) an (R) configuration; or -   (2) an (S) configuration.

In addition, the scope of the present invention also encompasses

-   (3) any mixtures of compounds of the formula (I) having an (R)     configuration (compounds of the formula (I-(R)) with compounds of     the formula (I) having an (S) configuration (compounds of the     formula (I-(S)),     where a racemic mixture of the compounds of the formula (I)     having (R) and (S) configuration is excluded from the present     invention.

Within the context of the present invention, preference is given to using in particular compounds of the formula (I) having (S) configuration (compounds of the formula (I-S)) compared to the (R) configuration (compounds of the formula (I-R)) with a selectivity of 60 to 100%, preferably 80 to 100%, in particular 90 to 100%, very particularly preferably 95 to 100%, where the particular (S) compound is present with an enantioselectivity of in each case more than 50% ee, preferably 60 to 100% ee, in particular 80 to 100% ee, very particularly 90 to 100% ee, most preferably 95 to 100% ee, based on the total content of (S) compound in question.

Accordingly, the present invention relates in particular to compounds of the formula (I) in which the stereochemical configuration on the sulfur atom marked by (*) is present with a stereochemical purity of 60 to 100% (S), preferably 80 to 100% (S), in particular 90 to 100% (S), very particularly 95 to 100% (S).

Depending on the type and attachment of the substituents, the compounds of the formula (I) may contain further centers of chirality in addition to the sulfur atom marked (*) in formula (I), in which case they are then present as stereoisomers. In the context of the present invention, the definition of the formula (I) comprises all stereoisomers, such as enantiomers, diasteromers and Z and E isomers, defined by their specific spatial form, i.e. the present invention comprises both the pure stereoisomers and less pure mixtures thereof. Here, preference is given in particular to compounds which, at the sulfur atom marked (*), have a stereochemical purity of from 60 to 100% (S), preferably from 80 to 100% (S), in particular from 90 to 100% (S), very particularly from 95 to 100% (S), and, at the remaining stereocenters, are present in racemic form or in a more or less pronounced stereochemical purity.

If, for example, one or more alkenyl groups are present, there may be diastereomers (Z and E isomers).

If, for example, one or more asymmetric carbon atoms are present, there may be enantiomers and diastereomers.

Corresponding stereoisomers may be obtained from the mixtures resulting from the preparation using customary separation methods, for example by chromatographic separation techniques. It is also possible to prepare stereoisomers selectively by using stereoselective reactions employing optically active starting materials and/or auxiliaries. Accordingly, the invention also relates to all stereoisomers embraced by the formula (I) but not shown in their specific stereoform, and to their mixtures.

For the possible combinations of the various substituents of the formula (I) the general principles of the construction of chemical compounds have to be observed, i.e. the formula (I) does not comprise any compounds known to the person skilled in the art as being chemically impossible.

The present invention furthermore provides processes for preparing corresponding compounds of the formula (I) and/or salts thereof and/or agrochemically acceptable quaternized nitrogen derivatives thereof:

-   a.) To prepare optically active sulfoxides of the formula (I), for     example, a thioether of the formula (II)

-   -   in which Y has the meanings given above for formula (I) is         oxidized with one equivalent of an oxidizing agent to the         sulfoxides (I):

-   -   The oxidizing agents which can be used for this reaction are not         subject to any particular requirements, and it is possible to         use any oxidizing agent capable of oxidizing the sulfur         compounds in question to sulfoxide compounds. Oxidizing agents         suitable for preparing the sulfoxides are inorganic peroxides,         such as, for example, hydrogen peroxide, sodium metaperiodate,         organic peroxides, such as, for example, tert-butyl         hydroperoxide, or organic peracids, such as peracetic acid or,         preferably, 3-chloroperbenzoic acid. The reaction can be carried         out in halogenated hydrocarbons, for example dichloromethane,         1,2-dichloroethane, an alcohol, such as, for example, methanol,         or in dimethylformamide, water or acetic acid, or in a mixture         of the solvents mentioned above. The reaction can be carried out         in a temperature range of between −80° C. and 120° C.,         preferably between −20° C. and 50° C. Such processes are known         in the literature and are described, for example, in J. Org.         Chem., 58 (1993) 2791, J. Org. Chem., 68 (2003) 3849 and J.         Heterocyclic Chem., 15 (1978) 1361, the relevant disclosure of         which is incorporated by reference into the present invention.     -   The preparation of the thioethers of the formula (II) is known,         for example, from JP 2003/096059 and WO 2006/123088.

-   b) Compounds of the formula (I) can additionally be prepared by     processes as described, for example, in JP 2003/096059 and WO     2006/123088, WO 2001/012613, WO 2002/062770, WO 2003/000686, WO     2003/010165, WO 2004/013106, WO 2006/024820, WO 2007/003294, WO     2007/003295.

-   c) The enantioselective synthesis of chiral sulfoxides of the     formula (I) in optically enriched or pure form can be carried out     from compounds of the general formula (II) using methods as     described, for example, in Chem. Rev., 103 (2003) 3651-3705 and the     literature cited therein, and Adv. Synth. Catal. 347 (2005) 19-31     and the literature cited therein. In each individual case, the     absolute configuration of the product depends on the structure of     the optically active catalyst.

Corresponding salts can be prepared in a manner known per se to the person skilled in the art.

Compounds of the formula (Ia)

consist of a mixture of the respective enantiomers (Ia-S) and (Ia-R) which are chiral at the sulfoxide function

where the radicals R¹, R², R³, R⁴, R⁵, R¹¹ and R¹² have the meanings given above for the formula (I).

Compounds of the formula (Ib)

consist of a mixture of the respective enantiomers (Ib-S) and (Ib-R) which are chiral at the sulfoxide function

where the radicals R⁶, R⁷, R⁸, R¹¹ and R¹² have the meanings given above for the formula (I).

Suitable for preparing enantiomers of the formula (I) are, in addition to enantioselective syntheses, also customary methods for the separation of racemates (cf. textbooks of stereochemistry).

Racemic mixtures, for example of optically active sulfoxides of the formula (I), can be separated by known processes. Such methods for the separation of racemates are described in handbooks of stereochemistry, for example in “Basic Organic Stereochemistry” (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Doyle, Michael P.; 2001; John Wiley & Sons) and “Stereochemisty of Organic Compounds (Eds.: Eliel, Ernest L.; Wilen, Samuel H.; Mander, Lewis N.; 1994; John Wiley & Sons), the relevant disclosure of which is incorporated by reference into the present invention. Suitable for this purpose are, for example, adduct formation with an optically active auxiliary reagent, separation of the diastereomeric adducts into the corresponding diastereomers, for example by crystallization, chromatographic methods, especially column chromatography and high pressure liquid chromatography, distillation, if appropriate under reduced pressure, extraction and other methods and subsequent cleavage of the diastereomers to afford the enantiomers. Suitable for preparative amounts or on an industrial scale are processes such as the crystallization of diastereomeric salts which can be obtained from the compounds (I) using optically active acids and, if appropriate, provided that acidic groups are present, using optically active bases.

Optically active acids which are suitable for racemate separation by crystallization of diastereomeric salts are, for example, camphorsulfonic acid, camphoric acid, bromocamphorsulfonic acid, quinic acid, tartaric acid, dibenzoyltartaric acid and other analogous acids; suitable optically active bases are, for example, quinine, cinchonine, quinidine, brucine, 1-phenylethylamine and other analogous bases.

The crystallizations are then in most cases carried out in aqueous or aqueous-organic solvents, where the diastereomer which is less soluble precipitates first, if appropriate after seeding. One enantiomer of the compound of the formula (I) is then liberated from the precipitated salt, or the other is liberated from the crystals, by acidification or using a base.

Furthermore, racemates can be separated chromatographically using chiral stationary phases. Such enantiomer separations can be carried out in the mg to 100 kg range using preparative HPLC units operated batchwise or continuously.

The “inert solvents” referred to in the above process variants are in each case solvents which are inert under the particular reaction conditions, i.e. do not react with the starting materials in particular, but need not be inert under all reaction conditions.

Libraries of compounds of the formula (I) and/or salts thereof which can be synthesized by the aforementioned reactions can also be prepared in a parallel manner, it being possible for this to take place in a manual, partly automated or completely automated manner. In this connection, it is, for example, possible to automate the reaction procedure, the work-up or the purification of the products and/or intermediates. Overall, this is understood as meaning a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry—Synthesis, Analysis, Screening (editor Günther Jung), Verlag Wiley 1999, on pages 1 to 34.

For the parallel reaction procedure and work-up, it is possible to use a series of commercially available instruments, for example Calypso reaction blocks from Barnstead International, Dubuque, Iowa 52004-0797, USA or reaction stations from Radleys, Shirehill, Saffron Walden, Essex, CB 11 3AZ, England or MultiPROBE Automated Workstations from Perkin Elmer, Waltham, Mass. 02451, USA. For the parallel purification of compounds of the formula (I) and salts thereof or of intermediates produced during the preparation, there are available, inter alia, chromatography apparatuses, for example from ISCO, Inc., 4700 Superior Street, Lincoln, Nebr. 68504, USA.

The apparatuses listed lead to a modular procedure in which the individual process steps are automated, but between the process steps manual operations have to be carried out. This can be circumvented by using partly or completely integrated automation systems in which the respective automation modules are operated, for example, by robots. Automation systems of this type can be acquired, for example, from Caliper, Hopkinton, Mass. 01748, USA.

The implementation of single or several synthesis steps can be supported through the use of polymer-supported reagents/scavenger resins. The specialist literature describes a series of experimental protocols, for example in Chem Files, Vol. 4, No. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).

Besides the methods described here, the preparation of compounds of the formula (I) and salts thereof can take place completely or partially by solid-phase supported methods. For this purpose, individual intermediates or all intermediates in the synthesis or a synthesis adapted for the corresponding procedure are bonded to a synthesis resin. Solid-phase supported synthesis methods are sufficiently described in the specialist literature, e.g. Barry A. Bunin in “The Combinatorial Index”, Verlag Academic Press, 1998 and Combinatorial Chemistry—Synthesis, Analysis, Screening (editor Günther Jung), Verlag Wiley, 1999. The use of solid-phase supported synthesis methods permits a series of protocols known in the literature, which again can be carried out manually or in an automated manner. For example, the “teabag method” (Houghten, U.S. Pat. No. 4,631,211; Houghten et al., Proc. Natl. Acad. Sci., 1985, 82, 5131-5135), in which products from IRORI, 11149 North Torrey Pines Road, La Jolla, Calif. 92037, USA, are employed, may be semiautomated. The automation of solid-phase supported parallel syntheses is performed successfully, for example, by apparatuses from Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, Calif. 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany. The reactions can be carried out, for example, by means of IRORI technology in microreactors from Nexus Biosystems, 12140 Community Road, Poway, Calif. 92064, USA.

Both on solid phase and in liquid phase, the procedure of individual or several synthesis steps can be supported through the use of microwave technology. The specialist literature describes a series of experimental protocols, for example in Microwaves in Organic and Medicinal Chemistry (editor C. O. Kappe and A. Stadler), Verlag Wiley, 2005.

The preparation according to the process described here produces compounds of the formula (I) and their salts in the form of substance collections which are called libraries.

The present invention also provides libraries which comprise at least two compounds of the formula (I) and their salts.

On account of the herbicidal property of the compounds of the formula (I), the invention also further provides the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants.

The compounds of the formula (I) according to the invention and their salts, also referred to synonymously below together as compounds of the formula (I), have excellent herbicidal efficacy against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Difficult-to-control perennial weeds which produce shoots from rhizomes, root stocks or other perennial organs are also well controlled by the active compounds. Here, it is immaterial whether the substances are applied by the presowing method, the pre-emergence method or the post-emergence method.

Specific examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds of the formula (I) according to the invention, without the enumeration being restricted to certain species.

On the side of the monocotyledonous weed species, e.g. Agrostis, Alopecurus, Apera, Avena, Brachicaria, Bromus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Festuca, Fimbristylis, Ischaemum, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Sagittaria, Scirpus, Setaria, Sphenoclea, and also Cyperus species predominantly from the annual group and on the sides of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperus species are well controlled.

In the case of dicotyledonous weed species, the spectrum of action extends to species such as, for example, Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual side, and Convolvulus, Cirsium, Rumex and Artemisia in the case of the perennial weeds. Moreover, herbicidal effect in the case of dicotyledonous weeds such as Ambrosia, Anthemis, Carduus, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Emex, Galeopsis, Galinsoga, Lepidium, Lindernia, Papaver, Portlaca, Polygonum, Ranunculus, Rorippa, Rotala, Seneceio, Sesbania, Solanum, Sonchus, Taraxacum, Trifolium, Urtica and Xanthium is observed.

If the compounds of the formula (I) according to the invention are applied to the soil surface before germination, the weed seedlings are either prevented completely from emerging or else the weeds grow until they have reached the cotyledon stage, but then their growth stops, and, eventually, after three to four weeks have elapsed, they die completely.

If the active compounds of the formula (I) are applied post-emergence to the green parts of the plants, growth likewise stops drastically a very short time after the treatment, and the weed plants remain at the growth stage at the point of time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crop plants, is eliminated very early and in a sustained manner.

Although the compounds of the formula (I) according to the invention have excellent herbicidal activity in respect of monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, such as, for example, wheat, barley, rye, rice, corn, sugarbeet, cotton, rapeseed and soybean, are only damaged negligibly, if at all.

This is why the present compounds are highly suitable for the selective control of unwanted plant growth in crops of agriculturally useful plants.

In addition, the substances of the formula (I) according to the invention have excellent growth regulatory properties in crop plants. They engage in the plant metabolism in a regulatory fashion and can therefore be employed for the influencing, in a targeted manner, of plant constituents and for facilitating harvesting, such as, for example, by triggering desiccation and stunted growth. Moreover, they are also suitable for generally controlling and inhibiting unwanted vegetative growth without destroying the plants in the process. Inhibiting the vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops since lodging can be reduced, or prevented completely, hereby.

By virtue of their herbicidal and plant-growth-regulatory properties, the active compounds can also be employed for controlling harmful plants in crops of known genetically modified plants or genetically modified plants still to be developed. In general, the transgenic plants are distinguished by especially advantageous properties, for example by resistances to certain pesticides, mainly certain herbicides, resistances to plant diseases or causative organisms of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other specific characteristics relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. Thus, transgenic plants are known whose starch content is increased, or whose starch quality is altered, or those where the harvested material has a different fatty acid composition. Other particular properties may be tolerance or resistance to abiotic stressors, for example heat, low temperatures, drought, salinity and ultraviolet radiation.

It is preferred to use the compounds of the formula (I) according to the invention or salts thereof in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, sorghum and millet, rice, cassaya and corn or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables.

It is preferred to employ the compounds of the formula (I) as herbicides in crops of useful plants which are resistant, or have been made resistant by recombinant means, to the phytotoxic effects of the herbicides.

Conventional methods of generating novel plants which have modified properties in comparison to plants occurring to date consist, for example, in traditional breeding methods and the generation of mutants. Alternatively, novel plants with altered properties can be generated with the aid of recombinant methods (see, for example, EP 0221044, EP 0131624). For example, the following have been described in several cases:

-   -   recombinant modifications of crop plants for the purposes of         modifying the starch synthesized in the plants (for example WO         92/011376, WO 92/014827, WO 91/019806),     -   transgenic crop plants which are resistant to certain herbicides         of the glufosinate type (cf., for example, EP 0242236,         EP 0242246) or the glyphosate type (WO 92/00377) or the         sulfonylurea type (EP 0257993, U.S. Pat. No. 5,013,659),     -   transgenic crop plants, for example cotton, which is capable of         producing Bacillus thuringiensis toxins (Bt toxins), which make         the plants resistant to certain pests (EP 0142924, EP 0193259),     -   transgenic crop plants with a modified fatty acid composition         (WO 91/013972).     -   genetically modified crop plants with novel constituents or         secondary metabolites, for example novel phytoalexins, which         bring about an increased disease resistance (EP 0309862, EP         0464461),     -   genetically modified plants with reduced photorespiration which         feature higher yields and higher stress tolerance (EP 0305398),     -   transgenic crop plants which produce pharmaceutically or         diagnostically important proteins (“molecular pharming”),     -   transgenic crop plants which are distinguished by higher yields         or better quality,     -   transgenic crop plants which are distinguished by a combination,         for example of the abovementioned novel properties (“gene         stacking”).

A large number of molecular-biological techniques by means of which novel transgenic plants with modified properties can be generated are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg. or Christou, “Trends in Plant Science” 1 (1996) 423-431).

To carry out such recombinant manipulations, nucleic acid molecules which allow mutagenesis or sequence changes by recombination of DNA sequences can be introduced into plasmids. For example, base substitutions can be carried out, part-sequences can be removed, or natural or synthetic sequences may be added with the aid of standard methods. To link the DNA fragments with one another, it is possible to add adapters or linkers to the fragments; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker “Gene and Klone”, VCH Weinheim 2nd ed., 1996.

For example, the generation of plant cells with a reduced activity of a gene product can be achieved by expressing at least one corresponding antisense RNA, a sense RNA for achieving a cosuppression effect or by expressing at least one suitably constructed ribozyme which specifically cleaves transcripts of the abovementioned gene product.

To this end, it is possible to use DNA molecules which encompass the entire coding sequence of a gene product inclusive of any flanking sequences which may be present, and also DNA molecules which only encompass portions of the coding sequence, it being necessary for these portions to be long enough to have an antisense effect in the cells. The use of DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical to them, is also possible.

When expressing nucleic acid molecules in plants, the protein synthesized can be localized in any desired compartment of the plant cell. However, to achieve localization in a particular compartment, it is possible, for example, to link the coding region with DNA sequences which ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The nucleic acid molecules can also be expressed in the organelles of the plant cells.

The transgenic plant cells can be regenerated by known techniques to give rise to entire plants. In principle, the transgenic plants can be plants of any desired plant species, i.e. not only monocotyledonous, but also dicotyledonous, plants.

Thus, transgenic plants can be obtained whose properties are altered by overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or the expression of heterologous (=foreign) genes or gene sequences.

It is preferred to employ the compounds of the formula (I) according to the invention in transgenic crops which are resistant to growth regulators such as, for example, dicamba, or against herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HP PD), or against herbicides from the group of the sulfonylureas, glyphosate, glufosinate or benzoylisoxazoles and analogous active substances.

When the active compounds of the formula (I) according to the invention are used in transgenic crops, effects are frequently observed—in addition to the effects on harmful plants which can be observed in other crops—which are specific for the application in the transgenic crop in question, for example a modified or specifically widened spectrum of weeds which can be controlled, modified application rates which may be employed for application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and an effect on growth and yield of the transgenic crop plants.

The invention therefore also relates to the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

The compounds of the formula (I) can be formulated in various ways according to which biological and/or physicochemical parameters are required. Possible formulations include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusting products (DP), seed-dressing products, granules for scattering and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.

These individual types of formulation are known in principle and are described, for example, in: Winnacker-Küchler, “Chemische Technologie” [Chemical technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, N.Y., 1973; K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation assistants, such as inert materials, surfactants, solvents and further additives, are likewise known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, “Grenzf{umlaut over (l)}achenaktive Äthylenoxidaddukte” [Interface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.

Based on these formulations, it is also possible to produce combinations with other pesticidally active compounds, such as, for example, insecticides, acaricides, herbicides, fungicides, and also with safeners, fertilizers and/or growth regulators, for example in the form of a finished formulation or as a tank mix.

Wettable powders are preparations which can be dispersed uniformly in water and, as well as the active compound, apart from a diluent or inert substance, also comprise surfactants of the ionic and/or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2′-dinaphthylmethane-6,6′-disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleylmethyltauride. To prepare the wettable powders, the herbicidally active compounds are ground finely, for example in customary apparatus such as hammer mills, blower mills and air-jet mills and simultaneously or subsequently mixed with the formulation assistants.

Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else relatively high-boiling aromatics or hydrocarbons or mixtures of the organic solvents with addition of one or more surfactants of the ionic and/or nonionic type (emulsifiers). The emulsifiers used may, for example, be: alkylarylsulfonic calcium salts, such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, such as, for example, sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, such as, for example, polyoxyethylene sorbitan fatty acid esters.

Dusts are obtained by grinding the active compound with finely distributed solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophillite, or diatomaceous earth.

Suspension concentrates may be water- or oil-based. They may be prepared, for example, by wet grinding by means of commercial bead mills and optional addition of surfactants as have, for example, already been listed above for the other formulation types.

Emulsions, e.g. oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and if appropriate surfactants, as have for example already been listed above in connection with the other types of formulation.

Granules can be prepared either by spraying the active compound onto granular inert material capable of adsorption or by applying active compound concentrates to the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in the manner customary for the preparation of fertilizer granules—if desired as a mixture with fertilizers.

Water-dispersible granules are prepared generally by the customary processes such as spray-drying, fluidized bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material. For the preparation of pan, fluidized bed, extruder and spray granules, see, for example, processes in “Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical and Engineering 1967, pages 147 ff; “Perry's Chemical Engineer's Handbook”, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

For further details regarding the formulation of crop protection compositions, see, for example, G. C. Klingman, “Weed Control as a Science”, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans, “Weed Control Handbook”, 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

The agrochemical formulations comprise generally from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula (I).

In wettable powders, the active compound concentration is, for example, from about 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation components. In the case of emulsifiable concentrates, the active compound concentration can be from about 1 to 90, preferably from 5 to 80, % by weight. Dust-type formulations contain from 1 to 30% by weight of active compound, preferably usually from 5 to 20% by weight of active compound; sprayable solutions contain from about 0.05 to 80% by weight, preferably from 2 to 50% by weight of active compound. In the case of water-dispersible granules, the active compound content depends partially on whether the active compound is present in liquid or solid form and on which granulation auxiliaries, fillers, etc., are used. In the water-dispersible granules, the content of active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

In addition, the active compound formulations mentioned optionally comprise the respective customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity.

The compounds of the formula (I) or salts thereof can be employed as such or in the form of their preparations (formulations) combined with other pesticidally active compounds, such as, for example, insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, for example as finished formulation or as tank mix. Combination partners which can be used for the active compounds of the formula (I) in mixture formulations or in the tank mix are, for example, known active compounds whose action is based on the inhibition of, for example, acetolactate synthase, acetyl-coenzyme-A carboxylase, PS I, PS II, HPPDO, phytoene desaturase, protoporphyrinogen oxidase, glutamine synthetase, 5-enolpyruvylshikimate 3-phosphate synthetase or cellulose biosynthesis. Such compounds and also other compounds that can be used, some of which having an unknown or other mechanism of action, are described, for example, in Weed Research 26, 441-445 (1986), or “The Pesticide Manual”, 11th edition 1997 (hereinbelow also referred to abbreviated as “PM”) and 12th edition 2000, The British Crop Protection Council and the Royal Soc. of Chemistry (publisher), and the literature cited therein. Herbicides known from the literature which can be combined with the compounds of the formula (I) are, for example, the following active compounds (note: the compounds are referred to either by the “common name” in accordance with the International Organization for Standardization (ISO) or by the chemical name, if appropriate together with a customary code number):

-   acetochlor; acifluorfen(-sodium); aclonifen; AKH 7088, i.e.     [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]acetic     acid and methyl     [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]acetate;     acrolein; alachlor; alloxydim(-sodium); ametryn; amicarbazone,     amidochlor, amidosulfuron; aminopyralid, amitrol; AMS, i.e. ammonium     sulfamate; anilofos; asulam; atraton; atrazine; azafenidin,     azimsulfuron (DPX-A8947); aziprotryn; barban; BAS 516 H, i.e.     5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; BCPC; beflubutamid,     benazolin(-ethyl); benfluralin; benfuresate; bensulfuron(-methyl);     bensulide; bentazone; benzfendizone; benzobicyclon, benzofenap;     benzofluor; benzoylprop(-ethyl); benzthiazuron; bifenox; bialaphos;     bifenox; bispyribac(-sodium), borax; bromacil; bromobutide;     bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone;     butachlor; butafenacil, butamifos; butenachlor; buthidazole;     butralin; butroxydim, butylate; cacodylic acid; calcium chlorate;     cafenstrole (CH-900); carbetamide; carfentrazone(-ethyl); caloxydim,     CDAA, i.e. 2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e.     2-chlorallyl diethyldithiocarbamate; chlorflurenol (-methyl);     chlomethoxyfen; clethodim; clomeprop; chloramben; chlorazifop-butyl,     chlormesulon; chlorbromuron; chlorbufam; chlorfenac;     chlorflurecol-methyl; chloridazon; chlorimuron(-ethyl); chloroacetic     acid; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham;     chlorsulfuron; chlorthal(-dimethyl); chlorthiamid; chlortoluron,     cinidon(-methyl and -ethyl), cinmethylin; cinosulfuron; cisanilide;     clefoxydim, clethodim; clodinafop and its ester derivatives (for     example clodinafop-propargyl); clomazone; clomeprop; cloproxydim;     clopyralid; clopyrasulfuron(-methyl); cloransulam(-methyl), cresol;     cumyluron (JC 940); cyanamide; cyanazine; cycloate; cyclosulfamuron     (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives     (for example the butyl ester, DEH-112); cyperquat; cyprazine;     cyprazole; daimuron; 2,4-D, 2,4-DB, 3,4-DA, 3,4-DB, 2,4-DEB,     dalapon; dazomed; desmedipham; desmetryn; di-allate; dicamba;     dichlobenil; ortho-dichlorobenzene; para-dichlorobenzene;     dichlorprop; dichlorprop-P; diclofop and its esters, such as     diclofop-methyl; diclosulam, diethatyl(-ethyl); difenoxuron;     difenzoquat; difenzoquat-methylsulfate; diflufenican; diflufenzopyr,     dimefuron; dimepiperate, dimethachlor; dimethametryn; dimethenamid     (SAN-582H); dimethenamid-P; dimethazone, dimexyflam, dimethipin;     dimethylarsinic acid; dimetrasulfuron, dinitramine; dinoseb;     dinoterb; diphenamid; dipropetryn; diquat; diquat-dibromide;     dithiopyr; diuron; DNOC; 3,4-DP; DSMA; EBEP; eglinazine-ethyl; EL77,     i.e.     5-cyano-1-(1,1-dimethylethyl)-N-methyl-1H-pyrazole-4-carboxamide;     endothal; epoprodan, EPTC; esprocarb; ethalfluralin;     ethametsulfuron(-methyl); ethidimuron; ethiozin; ethofumesate;     ethoxyfen and its esters (for example the ethyl ester, HN-252);     ethoxysulfuron, etobenzanid (HW 52); F5231, i.e.     N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]ethanesulfonamide;     fenoprop; fenoxan, fenoxapropand fenoxaprop-P and also their esters,     for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim;     fentrazamide, fenuron; ferrous sulfate; flamprop(-methyl or     -isopropyl or -isopropyl-L); flazasulfuron; floazulate, florasulam,     fluazifop and fluazifop-P and their esters, for example     fluazifop-butyl and fluazifop-P-butyl; fluazolate;     flucarbazone(-sodium), flucetosulfuron; fluchloralin; flufenacet;     flufenpyr(-ethyl); flumetsulam; flumeturon; flumiclorac(-pentyl),     flumioxazin (S-482); flumipropyn; fluometuron, fluorochloridone,     fluorodifen; fluoroglycofen(-ethyl); flupoxam (KNW-739); flupropacil     (UBIC-4243); flupropanate, flupyrsulfuron(-methyl or -sodium),     flurenol(-butyl), fluridone; fluorochloridone; fluoroxypyr(-meptyl);     flurprimidol; flurtamone; fluthiacet(-methyl) (KIH-9201);     fluthiamide; fomesafen; foramsulfuron; fosamine; furyloxyfen;     glufosinate(-ammonium); glyphosate(-isopropylammonium); halosafen;     halosulfuron(-methyl) and its esters (for example the methyl ester,     NC-319); haloxyfop and its esters; haloxyfop-P (=R-haloxyfop) and     its esters; HC-252; hexazinone; imazamethabenz(-methyl); imazapyr;     imazaquin and salts, such as the ammonium salt; imazamethapyr,     imazamox, imazapic, imazethamethapyr; imazethapyr; imazosulfuron;     indanofan, iodomethane; iodosulfuron(methylsodium); ioxynil;     isocarbamid; isopropalin; isoproturon; isouron; isoxaben;     isoxachlortole, isoxaflutole, isoxapyrifop; karbutilate; lactofen;     lenacil; linuron; MAA; MAMA; MCPA; MCPA-2-ethylhexyl;     MCPA-thioethyl; MCPB; mecoprop; mecoprop-P; mefenacet; mefluidid;     mesosulfuron(-methyl); mesotrione, metamifop; metamitron;     metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone;     methylarsonic acid; methyldymron; methyl isothiocyanate;     metabenzuron, metamifop; methobenzuron; metobromuron;     (alpha-)metolachlor; S-metolachlor; metosulam (XRD 511); metoxuron;     metribuzin; metsulfuron-methyl; MK-616; MH; molinate; monalide;     monocarbamide dihydrogensulfate; monolinuron; monuron; MSMA; MT 128,     i.e.     6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine;     MT 5950, i.e.     N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide;     naproanilide; napropamide; naptalam; NC 310, i.e.     4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon;     nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen;     nonanoic acid; norflurazon; oleic acid (fatty acid); orbencarb;     orthosulfamuron; oryzalin; oxadiargyl (RP-020630); oxadiazon;     oxasulfuron, oxaziclomefone, oxyfluorfen; paraquat;     paraquat-dichloride; pebulate; pelargonic acid, pendimethalin;     penoxsulam; pentachlorophenol; pentanochlor; pentoxazone,     perfluidone; phenisopham; phenmedipham(ethyl); pethoxamid; picloram;     picolinafen, pinoxaden, piperophos; piributicarb; pirifenop-butyl;     pretilachlor; primisulfuron(-methyl); potassium arsenite; potassium     azide; procarbazone-(sodium), procyazine; prodiamine; profluazol;     profluralin; profoxydim; proglinazine(-ethyl); prometon; prometryn;     propachlor; propanil; propaquizafop and its esters; propazine;     propham; propisochlor; propoxycarbazone(-sodium) (BAY MKH 6561);     propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005);     prynachlor; pyraclonil; pyraflufen(-ethyl), pyrasulfotole;     pyrazolinate; pyrazon; pyrazosulfuron(-ethyl); pyrazoxyfen;     pyribambenzisopropyl; pyribenzoxim, pyributicarb, pyridafol,     pyridate; pyriftalid; pyrimidobac(-methyl), pyrimisulfan,     pyrithiobac(-sodium) (KIN-2031); pyroxasulfone; pyroxofop and its     esters (for example the propargyl ester); pyroxsulam (triflosulam);     quinclorac; quinmerac; quinoclamine, quinofop and its ester     derivatives, quizalofop and quizalofop-P and their ester     derivatives, for example quizalofop-ethyl; quizalofop-P-tefuryl and     -ethyl; renriduron; rimsulfuron (DPX-E 9636); S 275, i.e.     2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4,5,6,7-tetrahydro-2H-indazole;     secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, i.e.     2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoic     acid and methyl     2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoate;     SMA; sodium arsenite; sodium azide; sodium chlorate; sulcotrione,     sulfentrazon (FMC-97285, F-6285); sulfazuron; sulfometuron(-methyl);     sulfosate (ICI-A0224); sulfosulfuron, 2,3,6-TBA; TCA(sodium);     tebutam (GCP-5544); tebuthiuron; tefuryltrione, tembotrione,     tepraloxydim, terbacil; terbucarb; terbuchlor; terbumeton;     terbuthylazine; terbutryn; TFH 450, i.e.     N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1H-1,2,4-triazole-1-carboxamide;     thenylchlor (NSK-850); thiafluamide, thiazafluoron; thiazopyr     (Mon-13200); thidiazimin (SN-24085); thiencarbazone-methyl,     thifensulfuron(-methyl); thiobencarb; tiocarbazil; tralkoxydim;     tri-allate; triasulfuron; triaziflam, triazofenamide;     tribenuron(-methyl); tricamba; triclopyr; tridiphane; trietazine;     trifloxysulfuron(sodium); trifluralin; triflusulfuron and esters     (for example the methyl ester, DPX-66037); trihydroxytriazine;     trimeturon; tritosulfuron; tropamezone; tsitodef; vernolate;     [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic     acid ethyl ester; WL 110547, i.e.     5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1H-tetrazole; UBH-509;     D-489; LS 82-556, i.e.     [(S)-3-N-(methylbenzyl)carbamoyl-5-propionyl-2,6-lutidine]; KPP-300;     NC-324; NC-330; KH-218; DPX-N8189; SC-0774; DOWCO-535; DK-8910;     V-53482; PP-600; MBH-001; ET-751, i.e. ethyl     [2-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl)-4-fluorophenoxy]acetate;     KIH-6127, i.e. pyriminobac-methyl; KIH-2023, i.e. bispyribac-sodium;     and SYP-249, i.e ethyl     2-{2-nitro-5-[(2-chloro-4-trifluoromethyl)phenoxy]benzoxy}-3-methyl-3-butenoate;     SYN-523.

Of particular interest is the selective control of harmful plants in crops of useful plants and ornamental plants. Although the compounds of the formula (I) according to the invention have already demonstrated very good to adequate selectivity in a large number of crops, in principle, in some crops and in particular also in the case of mixtures with other, less selective herbicides, phytotoxicities on the crop plants may occur. In this connection, combinations of compounds of the formula (I) according to the invention are of particular interest which comprise the compounds of the formula (I) or their combinations with other herbicides or pesticides and safeners. The safeners, which are used in an antidotically effective amount, reduce the phytotoxic side effects of the herbicides/pesticides employed, for example in economically important crops, such as cereals (wheat, barley, rye, corn, rice, sorghum and millet), sugar beet, sugar cane, oilseed rape, cotton and soybean, preferably cereals. The following groups of compounds are suitable, for example, as safeners for the compounds (I) alone or else in their combinations with further pesticides:

-   a) compounds of the formulae (S-II) to (S-IV)     where the symbols and indices have the following meanings:

-   n′ is a natural number from 0 to 5, preferably from 0 to 3; -   T is a (C₁- or C₂)-alkanediyl chain which is unsubstituted or     substituted by one or two (C₁-C₄)-alkyl radicals or by     [(C₁-C₃)-alkoxy]carbonyl; -   W is an unsubstituted or substituted divalent heterocyclic radical     from the group consisting of partially unsaturated or aromatic     five-membered heterocycles having 1 to 3 hetero ring atoms of the     type N or O, where at least one nitrogen atom and at most one oxygen     atom is present in the ring, preferably a radical from the group     consisting of (W1) to (W4),

-   m′ is 0 or 1; -   R¹⁷, R¹⁹ are identical or different and are halogen, (C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy, nitro or (C₁-C₄)-haloalkyl; -   R¹⁸, R²⁰ are identical or different and are OR²⁴, SR²⁴ or NR²⁴R²⁵ or     a saturated or unsaturated 3- to 7-membered heterocycle having at     least one nitrogen atom and up to 3 heteroatoms, preferably from the     group consisting of O and S, which is attached via the nitrogen atom     to the carbonyl group in (S-II) or (S-III) and is unsubstituted or     substituted by radicals from the group consisting of (C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy or optionally substituted phenyl, preferably a     radical of the formula OR²⁴, NHR²⁵ or N(CH₃)₂, in particular of the     formula OR²⁴; -   R²⁴ is hydrogen or an unsubstituted or substituted aliphatic     hydrocarbon radical having preferably a total of 1 to 18 carbon     atoms; -   R²⁵ is hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkoxy or substituted or     unsubstituted phenyl; -   R^(X′) is H, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl,     (C₁-C₄)-alkoxy-(C₁-C₈)-alkyl, cyano or COOR²⁶ where R²⁶ is hydrogen,     (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,     (C₁-C₆)-hydroxyalkyl, (C₃-C₁₂)-cycloalkyl or tri-(C₁-C₄)-alkylsilyl; -   R²⁷, R²⁸, R²⁹ are identical or different and are hydrogen,     (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl, (C₃-C₁₂)-cycloalkyl or substituted     or unsubstituted phenyl; -   R²¹ is (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₂-C₄)-alkenyl,     (C₂-C₄)-haloalkenyl, (C₃-C₇)-cycloalkyl, preferably dichloromethyl; -   R²², R²³ are identical or different and are hydrogen, (C₁-C₄)-alkyl,     (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-haloalkyl,     (C₂-C₄)-haloalkenyl, (C₁-C₄)-alkylcarbamoyl-(C₁-C₄)-alkyl,     (C₂-C₄)-alkenylcarbamoyl-(C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, dioxolanyl-(C₁-C₄)-alkyl, thiazolyl,     furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted     phenyl, or R²² and R²³ together form a substituted or unsubstituted     heterocyclic ring, preferably an oxazolidine, thiazolidine,     piperidine, morpholine, hexahydropyrimidine or benzoxazine ring; -   b) one or more compounds from the group consisting of:     -   1,8-naphthalic anhydride,     -   methyl diphenylmethoxyacetate,     -   1-(2-chlorobenzyl)-3-(1-methyl-1-phenylethyl)urea (cumyluron),     -   O,O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfoton),     -   4-chlorophenyl methylcarbamate (mephenate),     -   O,O-diethyl O-phenyl phosphorothioate (dietholate),     -   4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid (CL-304415,         CAS-Regno: 31541-57-8),     -   cyanomethoxyimino(phenyl)acetonitrile (cyometrinil)     -   1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil),     -   4′-chloro-2,2,2-trifluoroacetophenone         O-1,3-dioxolan-2-ylmethyloxime (fluxofenim),     -   4,6-dichloro-2-phenylpyrimidine (fenclorim),     -   benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate         (flurazole),     -   2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),     -   N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron),     -   (2,4-dichlorophenoxy)acetic acid (2,4-D),     -   (4-chlorophenoxy)acetic acid,     -   (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),     -   4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),     -   (4-chloro-o-tolyloxy)acetic acid (MCPA),     -   4-(4-chloro-o-tolyloxy)butyric acid,     -   4-(4-chlorophenoxy)butyric acid,     -   3,6-dichloro-2-methoxybenzoic acid (dicamba),     -   1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate         (lactidichlor)     -   and their salts and esters, preferably (C₁-C₈); -   c) N-acylsulfonamides of the formula (S-V) and their salts,

in which

-   R³⁰ is hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a     hydrocarbonthio radical or a heterocyclyl radical which is     preferably attached via a carbon atom, where each of the 4     last-mentioned radicals is unsubstituted or substituted by one or     more identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl,     carbonamide, sulfonamide and radicals of the formula —Z^(a′)—R^(a′),     -   where each hydrocarbon moiety has preferably 1 to 20 carbon         atoms and a carbon-containing radical R³⁰ including substituents         has preferably 1 to 30 carbon atoms; -   R³¹ is hydrogen or (C₁-C₄)-alkyl, preferably hydrogen, or -   R³⁰ and R³¹ together with the group of the formula —CO—N— are the     radicals of a 3- to 8-membered saturated or unsaturated ring; -   R³² are identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, CONH₂,     SO₂NH₂ or a radical of the formula —Z^(b′)—R^(b′); -   R³³ is hydrogen or (C₁-C₄)-alkyl, preferably H; -   R³⁴ are identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH₂, SO₂NH₂     and a radical of the formula —Z^(c′)—R^(c′); -   R^(a′) is a hydrocarbon radical or a heterocyclyl radical, where     each of the two last-mentioned radicals is unsubstituted or     substituted by one or more identical or different radicals from the     group consisting of halogen, cyano, nitro, amino, hydroxyl, mono-     and di-[(C₁-C₄)-alkyl]amino, or an alkyl radical in which a     plurality, preferably 2 or 3, non-adjacent CH₂ groups are in each     case replaced by an oxygen atom; -   R^(b′), R^(c′) are identical or different and are a hydrocarbon     radical or a heterocyclyl radical, where each of the two     last-mentioned radicals is unsubstituted or substituted by one or     more identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, phosphoryl,     halo-(C₁-C₄)-alkoxy, mono- and di-[(C₁-C₄)-alkyl]amino, or an alkyl     radical in which a plurality, preferably 2 or 3, non-adjacent CH₂     groups are in each case replaced by an oxygen atom; -   Z^(a′) is a divalent group of the formula —O—, —S—, —CO—, —CS—,     —CO—O—, —CO—S—, —O—CO—, —S—CO—, —SO—, —SO₂—, —NR*—, —CO—NR*—,     —NR*—CO—, —SO₂—NR*— or —NR*—SO₂—, where the bond indicated on the     right-hand side of the divalent group in question is the bond to the     radical R^(a)' and where the R* in the 5 last-mentioned radicals     independently of one another are each H, (C₁-C₄)-alkyl or     halo-(C₁-C₄)-alkyl; -   Z^(b′), Z^(c′) independently of one another are a direct bond or a     divalent group of the formula —O—, —S—, —CO—, —CS—, —CO—O—, —CO—S—,     —O—CO—, —S—CO—, —SO—, —SO₂—, —NR*—, —SO₂—NR*—, —NR*—SO₂—, —CO—NR*—     or —NR*—CO—, where the bond indicated on the right-hand side of the     divalent group in question is the bond to the radical R^(b′) or     R^(c′) and where the R* in the 5 last-mentioned radicals     independently of one another are each H, (C₁-C₄)-alkyl or     halo-(C₁-C₄)-alkyl; -   n is an integer from 0 to 4, preferably 0, 1 or 2, particularly     preferably 0 or 1, and -   m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular     0, 1 or 2; -   d) acylsulfamoylbenzamides of the formula (S-VI), if appropriate     also in salt form,

in which

-   X³ is CH or N, -   R³⁵ is hydrogen, heterocyclyl or a hydrocarbon radical, where the     two last-mentioned radicals are optionally substituted by one or     more identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH₂, SO₂NH₂     and Z^(a′)—R^(a′); -   R³⁶ is hydrogen, hydroxyl, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl,     (C₂-C₆)-alkynyl, (C₁-C₆)-alkoxy, (C₂-C₆)-alkenyloxy, where the five     last-mentioned radicals are optionally substituted by one or more     identical or different radicals from the group consisting of     halogen, hydroxyl, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and     (C₁-C₄)-alkylthio, or -   R³⁵ and R³⁶ together with the nitrogen atom that carries them are a     3- to 8-membered saturated or unsaturated ring; -   R³⁷ is halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH₂,     SO₂NH₂ or Z^(b′)—R^(b′); -   R³⁸ is hydrogen, (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl or (C₂-C₄)-alkynyl; -   R³⁹ is halogen, cyano, nitro, amino, hydroxyl, carboxyl, phosphoryl,     CHO, CONH₂, SO₂NH₂ or Z^(c′)—R^(c′); -   R^(a′) is a (C₂-C₂₀)-alkyl radical whose carbon chain is interrupted     once or more than once by oxygen atoms, is heterocyclyl or a     hydrocarbon radical, where the two last-mentioned radicals are     optionally substituted by one or more identical or different     radicals from the group consisting of halogen, cyano, nitro, amino,     hydroxyl, mono- and di-[(C₁-C₄)-alkyl]amino; -   R^(b′), R^(c′) are identical or different and are a (C₂-C₂₀)-alkyl     radical whose carbon chain is interrupted once or more than once by     oxygen atoms, are heterocyclyl or a hydrocarbon radical, where the     two last-mentioned radicals are optionally substituted by one or     more identical or different radicals from the group consisting of     halogen, cyano, nitro, amino, hydroxyl, phosphoryl,     (C₁-C₄)-haloalkoxy, mono- and di-[(C₁-C₄)-alkyl]amino; -   Z^(a′) is a divalent unit from the group consisting of O, S, CO, CS,     C(O)O, C(O)S, SO, SO₂, NR^(d′), C(O)NR^(d′) and SO₂NR^(d′); -   Z^(b′), Z^(c′) are identical or different and are a direct bond or a     divalent unit from the group consisting of O, S, CO, CS, C(O)O,     C(O)S, SO, SO₂, NR^(d′), SO₂NR^(d′) and C(O)NR^(d′); -   R^(d′) is hydrogen, (C₁-C₄)-alkyl or (C₁-C₄)-haloalkyl; -   N is an integer from 0 to 4, and -   m, if X is CH, is an integer from 0 to 5, and, if X is N, is an     integer from 0 to 4; -   e) compounds of the type of the acylsulfamoylbenzamides, for example     of the formula (S-VII) below, which are known, for example, from WO     99/16744,

for example those in which

-   -   R²¹=cyclopropyl and         R²²=H(S-3-1=4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzenesulfonamide),     -   R²¹=cyclopropyl and R²²=5-Cl (S-3-2),     -   R²¹=ethyl and R²²=H(S-3-3),     -   R²¹=isopropyl and R²²=5-Cl (S-3-4) and     -   R²¹=isopropyl and R²²=H(S-3-5);

-   f) compounds of the type of the N-acylsulfamoylphenylureas of the     formula (S-VIII), which are known, for example, from EP-A-365484

in which

-   A is a radical from the group consisting of

-   R^(α′) and R^(β′) independently of one another are hydrogen,     (C₁-C₈)-alkyl, (C₃-C₈)-cycloalkyl, (C₃-C₆)-alkenyl, (C₃-C₆)-alkynyl,

or (C₁-C₄)-alkoxy substituted by (C₁-C₄)-alkoxy or

-   R^(α′) and R^(β′) together are a (C₄-C₆)-alkylene bridge or a     (C₄-C₆)-alkylene bridge which is interrupted by oxygen, sulfur, SO,     SO₂, NH or —N((C₁-C₄)-alkyl)-, -   R^(γ′) is hydrogen or (C₁-C₄)-alkyl, -   R^(a′) and R^(b′) independently of one another are hydrogen,     halogen, cyano, nitro, trifluoromethyl, (C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, —COOR^(j), —CONR^(k′)R^(m′), —COR^(n′),     —SO₂NR^(k′)R^(m′) or —OSO₂—(C₁-C₄)-alkyl, or R^(a′) and R^(b′)     together are a (C₃-C₄)-alkylene bridge which may be substituted by     halogen or (C₁-C₄)-alkyl, or a (C₃-C₄)-alkenylene bridge which may     be substituted by halogen or (C₁-C₄)-alkyl, or a C₄-alkadienylene     bridge which may be substituted by halogen or (C₁-C₄)-alkyl, and -   R^(g′) and R^(h′) independently of one another are hydrogen,     halogen, (C₁-C₄)-alkyl, trifluoromethyl, methoxy, methylthio or     —COOR^(j′), where -   R^(c′) is hydrogen, halogen, (C₁-C₄)-alkyl or methoxy, -   R^(d′) is hydrogen, halogen, nitro, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,     (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylsulfonyl,     —COOR^(j′) or —CONR^(k′)R^(m′), -   R^(e′) is hydrogen, halogen, (C₁-C₄)-alkyl, —COOR^(j),     trifluoromethyl or methoxy, or R^(d′) and R^(e′) together are a     (C₃-C₄)-alkylene bridge, -   R^(f′) is hydrogen, halogen or (C₁-C₄)-alkyl, -   R^(X′) and R^(Y′) independently of one another are hydrogen,     halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylthio,     —COOR^(j′), trifluoromethyl, nitro or cyano, -   R^(j′), R^(k′) and R^(m′) independently of one another are hydrogen     or (C₁-C₄)-alkyl, -   R^(k′) and R^(m′) together are a C₄-C₆-alkylene bridge or a     (C₄-C₆)-alkylene bridge which is interrupted by oxygen, NH or     —N((C₁-C₄)-alkyl)-, and -   R^(n′) is (C₁-C₄)-alkyl, phenyl or phenyl which is substituted by     halogen, (C₁-C₄)-alkyl, methoxy, nitro or trifluoromethyl,     preferably     -   1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,     -   1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,     -   1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,     -   1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea, -   g) compounds of the type of the acylsulfamoylbenzamides of the     formula (S-IX), known from EP-A-1019368, if appropriate also in salt     form,

in which

-   R¹⁰¹ is methyl, methoxy or trifluoromethoxy; -   R¹⁰² is hydrogen, chlorine or methyl; -   R¹⁰³ is hydrogen, ethyl or propargyl; -   R¹⁰⁴ is ethyl, cyclopropyl, isopropyl or propargyl, or -   R¹⁰³ and R¹⁰⁴ together form the group (CH₂)₄,     including the stereoisomers, and the salts customary in agriculture.

Preference is given to herbicide-safener combinations comprising (A) a herbicidally effective amount of one or more compounds of the formula (I) or salts thereof and (B) an amount, acting as an antidote, of one or more safeners.

Herbicidally effective amount in the sense of the invention is an amount of one or more herbicides sufficient to have an adverse impact on plant growth. In the sense of the invention, an amount which acts as an antidote is an amount of one or more safeners sufficient to reduce the phytotoxic action of crop protection agents (for example herbicides) in crop plants.

The compounds of the formula (S-II) are known, for example, from EP-A-0 333 131 (ZA-89/1960), EP-A-0 269 806 (U.S. Pat. No. 4,891,057), EP-A-0 346 620 (AU-A-89/34951), EP-A-0 174 562, EP-A-0 346 620 (WO-A-91/08 202), WO-A-91/07 874 or WO-A 95/07 897 (ZA 94/7120) and the literature cited therein or can be prepared by or analogously to the processes described therein. The compounds of the formula (S-III) are known from EP-A-0 086 750, EP-A-0 94349 (U.S. Pat. No. 4,902,340), EP-A-0 191736 (U.S. Pat. No. 4,881,966) and EP-A-0 492 366 and the literature cited therein or can be prepared by or analogously to the processes described therein. Furthermore, some compounds are described in EP-A-0 582 198 and WO 2002/34048.

The compounds of the formula (S-IV) are known from numerous patent applications, for example U.S. Pat. Nos. 4,021,224 and 4,021,229.

Compounds of the group B (b) are furthermore known from CN-A-87/102 789, EP-A-365484 and from “The Pesticide Manual”, The British Crop Protection Council and the Royal Society of Chemistry, 11th edition, Farnham 1997.

The compounds of the group B (c) are described in WO-A-97/45016, those of group B (d) in WO-A-99/16744, those of group B (e) in EP-A-365484 and those of group B (g) in EP-A-1019368.

The publications cited contain detailed statements about preparation processes and starting materials and mention preferred compounds. These publications are expressly referred to; by reference, they form part of the present description.

Preference is given to herbicide-safener combinations comprising safeners of the formula (S-II) and/or (S-III) in which the symbols and indices are as defined below:

-   R²⁴ is hydrogen, (C₁-C₁₈)-alkyl, (C₃-C₁₂)-cycloalkyl,     (C₂-C₈)-alkenyl and (C₂-C₁₈)-alkynyl, where the carbon-containing     groups may be substituted by one or more, preferably up to three,     radicals R⁵⁰; -   R⁵⁰ are identical or different and are halogen, hydroxyl,     (C₁-C₈)-alkoxy, (C₁-C₈)-alkylthio, (C₂-C₈)-alkenylthio,     (C₂-C₈)-alkynylthio, (C₂-C₈)-alkenyloxy, (C₂-C₈)-alkynyloxy,     (C₃-C₇)-cycloalkyl, (C₃-C₇)-cycloalkoxy, cyano, mono- and     di(C₁-C₄)-alkylamino, carboxyl, (C₁-C₈)-alkoxycarbonyl,     (C₂-C₈)-alkenyloxycarbonyl, (C₁-C₈)-alkylthiocarbonyl,     (C₂-C₈)-alkynyloxycarbonyl, (C₁-C₈)-alkylcarbonyl,     (C₂-C₈)-alkenylcarbonyl, (C₂-C₈)-alkynylcarbonyl,     1-(hydroxyimino)-(C₁-C₈)-alkyl,     1-[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl,     1-[(C₁-C₄)-alkoxyimino]-(C₁-C₈)-alkyl, (C₁-C₈)-alkylcarbonylamino,     (C₂-C₈)-alkenylcarbonylamino, (C₂-C₈)-alkynylcarbonylamino,     aminocarbonyl, (C₁-C₈)-alkylaminocarbonyl,     di-(C₁-C₆)-alkylaminocarbonyl, (C₂-C₆)-alkenylaminocarbonyl,     (C₂-C₆)-alkynylaminocarbonyl, (C₁-C₈)-alkoxycarbonylamino,     (C₁-C₈)-alkylaminocarbonylamino, (C₁-C₆)-alkylcarbonyloxy which is     unsubstituted or substituted by R⁵¹, (C₂-C₆)-alkenylcarbonyloxy,     (C₂-C₆)-alkynylcarbonyloxy, (C₁-C₈)-alkylsulfonyl, phenyl,     phenyl-(C₁-C₈)-alkoxy, phenyl-(C₁-C₆)-alkoxycarbonyl, phenoxy,     phenoxy-(C₁-C₈)-alkoxy, phenoxy-(C₁-C₆)-alkoxycarbonyl,     phenylcarbonyloxy, phenyl-carbonylamino,     phenyl-(C₁-C₆)-alkylcarbonylamino, where the phenyl ring of the 9     last-mentioned radicals is unsubstituted or mono- or     polysubstituted, preferably up to trisubstituted, by radicals R⁵²;     SiR′₃, —O—SiR′₃, R′₃Si—(C₁-C₈)-alkoxy, —CO—O—NR′₂, —O—N═CR′₂,     —N═CR′₂, —O—NR′₂, —NR′₂, CH(OR′)₂, —O—(CH₂)_(m)—CH(OR)₂,     —CR′″(OR′)₂, —O—(CH₂)_(m)CR′″(OR″)₂ or by     R″O—CHR′″CHCOR″—(C₁-C₆)-alkoxy, -   R⁵¹ are identical or different and are halogen, nitro,     (C₁-C₄)-alkoxy and phenyl which is unsubstituted or substituted by     one or more, preferably up to three, radicals R⁵²; -   R⁵² are identical or different and are halogen, (C₁-C₄)-alkyl,     (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy or nitro; -   R′ are identical or different and are hydrogen, (C₁-C₄)-alkyl,     phenyl which is unsubstituted or substituted by one or more,     preferably up to three, radicals R⁵², or two radicals R′ together     form a (C₂-C₆)-alkanediyl chain; -   R″ are identical or different and are (C₁-C₄)-alkyl, or two radicals     R″ together form a (C₂-C₆)-alkanediyl chain; -   R′″ is hydrogen or (C₁-C₄)-alkyl; -   m is 0, 1, 2, 3, 4, 5 or 6.

Particular preference is given to herbicide-safener combinations according to the invention comprising safeners of the formula (S-II) and/or (S-III) in which the symbols and indices are as defined below:

-   R²⁴ is hydrogen, (C₁-C₈)-alkyl or (C₃-C₇)-cycloalkyl, where the     carbon-containing radicals above are unsubstituted or mono- or     polysubstituted by halogen or mono- or disubstituted, preferably     monosubstituted, by radicals R⁵⁰, -   R⁵⁰ are identical or different and are hydroxyl, (C₁-C₄)-alkoxy,     carboxyl, (C₁-C₄)-alkoxycarbonyl, (C₂-C₆)-alkenyloxycarbonyl,     (C₂-C₆)-alkynyloxycarbonyl, 1-(hydroxyimino)-(C₁-C₄)-alkyl,     1-[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl and     1-[(C₁-C₄)-alkoxyimino]-(C₁-C₄)-alkyl; —SiR′₃, —O—N═CR′₂, —N═CR′₂,     —NR′₂ and —O—NR′₂, in which R′ are identical or different and are     hydrogen, (C₁-C₄)-alkyl or, as a pair, are a (C₄-C₅)-alkanediyl     chain, -   R²⁷, R²⁸, R²⁹ are identical or different and are hydrogen,     (C₁-C₈)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₇)-cycloalkyl or phenyl which     is unsubstituted or substituted by one or more radicals from the     group consisting of halogen, cyano, nitro, amino, mono- and     di-[(C₁-C₄)-alkyl]amino, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio and     (C₁-C₄)-alkylsulfonyl; -   R^(x′) is hydrogen or COOR²⁴, where R²⁶ is hydrogen, (C₁-C₈)-alkyl,     (C₁-C₈)-haloalkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,     (C₁-C₆)-hydroxyalkyl, (C₃-C₇)-cycloalkyl or tri-(C₁-C₄)-alkylsilyl, -   R¹⁷, R¹⁹ are identical or different and are halogen, methyl, ethyl,     methoxy, ethoxy, (C₁-C₂)-haloalkyl, preferably hydrogen, halogen or     (C₁-C₂)-haloalkyl.

Very particular preference is given to safeners in which the symbols and indices in the formula (S-II) are as defined below:

-   R¹⁷ is halogen, nitro or (C₁-C₄)-haloalkyl; -   n′ is 0, 1, 2 or 3; -   R¹⁸ is a radical of the formula OR²⁴, -   R²⁴ is hydrogen, (C₁-C₈)-alkyl or (C₃-C₇)-cycloalkyl, where the     carbon-containing radicals above are unsubstituted or mono- or     polysubstituted, preferably up to trisubstituted, by identical or     different halogen radicals or up to disubstituted, preferably     monosubstituted, by identical or different radicals from the group     consisting of hydroxyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkoxycarbonyl,     (C₂-C₆)-alkenyloxycarbonyl, (C₂-C₆)-alkynyloxycarbonyl,     1-(hydroxyimino)-(C₁-C₄)-alkyl,     1-[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl,     1-[(C₁-C₄)-alkoxyimino]-(C₁-C₄)-alkyl and radicals of the formulae     —SiR′₃, —O—N═R′₂, —N═CR′₂, —NR′₂ and —O—NR′₂, where the radicals R′     in the formulae mentioned are identical or different and are     hydrogen, (C₁-C₄)-alkyl or, as a pair, are (C₄-C₅)-alkanediyl; -   R²⁷, R²⁸, R²⁹ are identical or different and are hydrogen,     (C₁-C₈)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₇)-cycloalkyl or phenyl which     is unsubstituted or substituted by one or more radicals from the     group consisting of halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro,     (C₁-C₄)-haloalkyl and (C₁-C₄)-haloalkoxy, and -   R^(x′) is hydrogen or COOR²⁶, where R²⁶ is hydrogen, (C₁-C₈)-alkyl,     (C₁-C₈)-haloalkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,     (C₁-C₆)-hydroxyalkyl, (C₃-C₇)-cycloalkyl or tri-(C₁-C₄)-alkylsilyl.

Very particular preference is also given to safeners of the formula (S-III) in which the symbols and indices are as defined below:

-   R¹⁹ is halogen or (C₁-C₄)-haloalkyl; -   n′ is 0, 1, 2 or 3, where (R¹⁹)_(n′) is preferably 5-Cl; -   R²⁰ is a radical of the formula OR²⁴; -   T is CH₂ or CH(COO—((C₁-C₃)-alkyl)) and -   R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl or     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, preferably hydrogen or (C₁-C₈)-alkyl.

Especially preferred are safeners of the formula (II) in which the symbols and indices are as defined below:

-   W is (W1); -   R¹⁷ is halogen or (C₁-C₂)-haloalkyl; -   n′ is 0, 1, 2 or 3, where (R¹⁷)_(n′) is preferably 2,4-Cl₂; -   R¹⁸ is a radical of the formula OR²⁴; -   R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-hydroxyalkyl, (C₃-C₇)-cycloalkyl,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl or tri-(C₁-C₂)-alkylsilyl, preferably     (C₁-C₄)-alkyl; -   R²⁷ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl or     (C₃-C₇)-cycloalkyl, preferably hydrogen or (C₁-C₄)-alkyl, and -   R^(x′) is COOR²⁶, where R²⁶ is hydrogen, (C₁-C₈)-alkyl,     (C₁-C₄)-haloalkyl, (C₁-C₄)-hydroxyalkyl, (C₃-C₇)-cycloalkyl,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl or tri-(C₁-C₂)-alkylsilyl, preferably     hydrogen or (C₁-C₄)-alkyl.

Also especially preferred are herbicidal compositions comprising a safener of the formula (S-II) in which the symbols and indices are as defined below:

-   W is (W2); -   R¹⁷ is halogen or (C₁-C₂)-haloalkyl; -   n′ is 0, 1, 2 or 3, where (R¹⁷)_(n′) is preferably 2,4-Cl₂; -   R¹⁸ is a radical of the formula OR²⁴; -   R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-hydroxyalkyl, (C₃-C₇)-cycloalkyl,     ((C₁-C₄)-alkoxy)-(C₁-C₄)-alkyl or tri-(C₁-C₂)-alkylsilyl, preferably     (C₁-C₄)-alkyl; -   R²⁷ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,     (C₃-C₇)-cycloalkyl or unsubstituted or substituted phenyl,     preferably hydrogen, (C₁-C₄)-alkyl or phenyl which is unsubstituted     or substituted by one or more radicals from the group consisting of     halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, nitro, cyano and     (C₁-C₄)-alkoxy.

Especially preferred are also safeners of the formula (S-II) in which the symbols and indices are as defined below:

-   W is (W3); -   R¹⁷ is halogen or (C₁-C₂)-haloalkyl; -   n′ is 0, 1, 2 or 3, where (R¹⁷)_(n′) is preferably 2,4-Cl₂; -   R¹⁸ is a radical of the formula OR²⁴; -   R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-hydroxyalkyl, (C₃-C₇)-cycloalkyl,     (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl or tri-(C₁-C₂)-alkylsilyl, preferably     (C₁-C₄)-alkyl, and -   R²⁸ is (C₁-C₈)-alkyl or (C₁-C₄)-haloalkyl, preferably C₁-haloalkyl.

Especially preferred are also safeners of the formula (S-II) in which the symbols and indices are as defined below:

-   W is (W4); -   R¹⁷ is halogen, nitro, (C₁-C₄)-alkyl, (C₁-C₂)-haloalkyl, preferably     CF₃, or (C₁-C₄)-alkoxy; -   n′ is 0, 1, 2 or 3; -   m′ is 0 or 1; -   R¹⁸ is a radical of the formula OR²⁴; -   R²⁴ is hydrogen, (C₁-C₄)-alkyl, carboxy-(C₁-C₄)-alkyl,     (C₁-C₄)-alkoxycarbonyl-(C₁-C₄)-alkyl, preferably     (C₁-C₄)-alkoxy-CO—CH₂, (C₁-C₄)-alkoxy-CO—C(CH₃)H—, HO—CO—CH₂— or     HO—CO—C(CH₃)H , and -   R²⁹ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,     (C₃-C₇)-cycloalkyl or phenyl which is unsubstituted or substituted     by one or more radicals from the group consisting of halogen,     (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, nitro, cyano and (C₁-C₄)-alkoxy.

Particularly suitable as safeners for the herbicidally active compounds of the formula (I) are the following groups of compounds:

-   b) compounds of the type of the     dichlorophenylpyrazoline-3-carboxylic acid (i.e. of the formula     (S-II) in which W═(W1) and (R¹⁷)_(n′)=2,4-Cl₂), preferably compounds     such as ethyl     1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate     (S-II-1, mefenpyr-diethyl), mefenpyr-dimethyl and mefenpyr (S-II-0),     and related compounds as described in WO-A 91/07874; -   c) derivatives of dichlorophenylpyrazolecarboxylic acid (i.e. of the     formula (S-II) in which W═(W2) and (R¹⁷)_(n′)=2,4-Cl₂), preferably     compounds such as ethyl     1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (S-II-2),     ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate     (S-II-3), ethyl     1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate     (S-II-4), ethyl     1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S-II-5) and     related compounds, as described in EP-A-0 333 131 and EP-A-0 269     806; -   d) compounds of the type of the triazolecarboxylic acids (i.e. of     the formula (S-II) in which W═(W3) and (R¹⁷)_(n′)=2,4-Cl₂),     preferably compounds such as fenchlorazole-ethyl, i.e. ethyl     1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate     (S-II-6), and related compounds (see EP-A-0 174 562 and EP-A-0 346     620); -   e) compounds of the type of the 5-benzyl- or     5-phenyl-2-isoxazoline-3-carboxylic acid or of the     5,5-diphenyl-2-isoxazoline-3-carboxylic acid, such as isoxadifen     (S-II -12), (in which W═(W4)), preferably compounds such as ethyl     5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S-II-7) or ethyl     5-phenyl-2-isoxazoline-3-carboxylate (S-II-8) and related compounds,     as described in WO-A-91/08202, or of ethyl     5,5-diphenyl-2-isoxazolinecarboxylate (S-II-9, isoxadifen-ethyl) or     n-propyl 5,5-diphenyl-2-isoxazolinecarboxylate (S-II-10) or of ethyl     5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S-II-11),     as described in WO-A-95/07897. -   f) of the type of the 8-quinolineoxyacetic acid, for example those     of the formula (S-III) in which (R¹⁹)_(n′)=5-Cl, R²⁰═OR²⁴ and T=CH₂,     preferably the compounds     -   1-methylhexyl (5-chloro-8-quinolineoxy)acetate (S-III-1,         cloquintocet-mexyl),     -   1,3-dimethylbut-1-yl (5-chloro-8-quinolineoxy)acetate (S-III-2),     -   4-allyloxybutyl (5-chloro-8-quinolineoxy)acetate (S-III-3),     -   1-allyloxyprop-2-yl (5-chloro-8-quinolineoxy)acetate (S-III-4),     -   ethyl (5-chloro-8-quinolineoxy)acetate (S-III-5),     -   methyl (5-chloro-8-quinolineoxy)acetate (S-III-6),     -   allyl (5-chloro-8-quinolineoxy)acetate (S-III-7),     -   2-(2-propylideneiminoxy)-1-ethyl         (5-chloro-8-quinolineoxy)acetate (S-III-8),     -   2-oxoprop-1-yl(5-chloro-8-quinolineoxy)acetate (S-III-9),     -   (5-chloro-8-quinolineoxy)acetic acid (S-III-10) and its salts,         as described, for example, in WO-A-2002/34048,     -   and related compounds as described in EP-A-0 860 750, EP-A-0 094         349 and EP-A-0 191 736 or EP-A-0 492 366. -   g) Compounds of the type of the (5-chloro-8-quinolineoxy)malonic     acid, i.e. of the formula (S-III) in which (R¹⁹)_(n′)=5-Cl,     R²⁰═OR²⁴, T=—CH(COO-alkyl)-, preferably the compounds diethyl     (5-chloro-8-quinolineoxy)malonate (S-III-11), diallyl     (5-chloro-8-quinolineoxy)-malonate, methyl ethyl     (5-chloro-8-quinolineoxy)malonate and related compounds, as     described in EP-A-0 582 198. -   h) Compounds of the type of the dichloroacetamide, i.e. of the     formula (S-IV), preferably:     -   N,N-diallyl-2,2-dichloroacetamide (dichlormid (S-IV-1), from         U.S. Pat. No. 4,137,070),         4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (IV-2,         benoxacor, from EP 0 149 974),     -   N1,N2-diallyl-N2-dichloroacetylglycinamide (DKA-24 (IV-3), from         HU 2143821),     -   4-dichloroacetyl-1-oxa-4-azaspiro[4,5]decane (AD-67),     -   2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide         (PPG-1292),     -   3-dichloroacetyl-2,2,5-trimethyloxazolidine (R-29148, S-IV-4),     -   3-dichloroacetyl-2,2-dimethyl-5-phenyloxazolidine,     -   3-dichloroacetyl-2,2-dimethyl-5-(2-thienyl)oxazolidine,     -   3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine         (furilazole (S-IV-5), MON 13900),     -   1-dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo[1,2-a]pyrimidin-6(2H)-one         (dicyclonon, BAS 145138). -   i) Compounds of the group B(b), preferably     -   1,8-naphthalic anhydride (S-b-1),     -   methyl diphenylmethoxyacetate (S-b-2),     -   cyanomethoxyimino(phenyl)acetonitrile (cyometrinil) (S-b-3),     -   1-(2-chlorobenzyl)-3-(1-methyl-1-phenylethyl)urea (cumyluron)         (S-b-4),     -   O,O-diethyl S-2-ethylthioethyl phosphorodithioate (disulfoton)         (S-b-5),     -   4-chlorophenyl methylcarbamate (mephenate) (S-b-6),     -   O,O-diethyl O-phenyl phosphorothioate (dietholate) (S-b-7),     -   4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid (CL-304415,         CAS-Regno: 31541-57-8) (S-b-8),     -   1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil)         (S-b-9),     -   4′-chloro-2,2,2-trifluoroacetophenone         O-1,3-dioxolan-2-ylmethyloxime (fluxofenim) (S-b-10),     -   4,6-dichloro-2-phenylpyrimidine (fenclorim) (S-b-11),     -   benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate         (flurazole) (S-b-12),     -   2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191) (S-b-13),     -   N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron)         (S-b-14),     -   (2,4-dichlorophenoxy)acetic acid (2,4-D),     -   (4-chlorophenoxy)acetic acid,     -   (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),     -   4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),     -   (4-chloro-o-tolyloxy)acetic acid (MCPA),     -   4-(4-chloro-o-tolyloxy)butyric acid,     -   4-(4-chlorophenoxy)butyric acid,     -   3,6-dichloro-2-methoxybenzoic acid (dicamba),     -   1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate         (lactidichlor) and their salts and esters, preferably their         (C₁-C₈)-esters.

Preferred as safeners are furthermore compounds of the formula (S-V) or salts thereof in which

-   R³⁰ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, furanyl or     thienyl, where each of the 4 last-mentioned radicals is     unsubstituted or substituted by one or more substituents from the     group consisting of halogen, (C₁-C₄)-alkoxy, halo-(C₁-C₆)-alkoxy and     (C₁-C₄)-alkylthio and, in the case of cyclic radicals, also     (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl, -   R³¹ is hydrogen, -   R³² is halogen, halo-(C₁-C₄)-alkyl, halo-(C₁-C₄)-alkoxy,     (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylcarbonyl, preferably halogen,     (C₁-C₄)-haloalkyl, such as trifluoromethyl, (C₁-C₄)-alkoxy,     halo-(C₁-C₄)-alkoxy, (C₁-C₄)-alkoxycarbonyl or     (C₁-C₄)-alkylsulfonyl, -   R³³ is hydrogen, -   R³⁴ is halogen, (C₁-C₄)-alkyl, halo-(C₁-C₄)-alkyl,     halo-(C₁-C₄)-alkoxy, (C₃-C₆)-cycloalkyl, phenyl, (C₁-C₄)-alkoxy,     cyano, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkoxycarbonyl or     (C₁-C₄)-alkylcarbonyl, preferably halogen, (C₁-C₄)-alkyl,     (C₁-C₄)-haloalkyl, such as trifluoromethyl, halo-(C₁-C₄)-alkoxy,     (C₁-C₄)-alkoxy or (C₁-C₄)-alkylthio, -   n is 0, 1 or 2 and -   m is 1 or 2.

Particular preference is given to compounds of the formula (S-V) in which

-   R³⁰═H₃C—O—CH₂—, R³¹═R³³═H, R³⁴=2-OMe (S-V-1), -   R³⁰═H₃C—O—CH₂—, R³¹═R³³═H, R³⁴=2-OMe-5-Cl (S-V-2), -   R³⁰=cyclopropyl, R³¹═R³³═H, R³⁴=2-OMe (S-V-3), -   R³⁰=cyclopropyl, R³¹═R³³=H, R³⁴=2-OMe-5-Cl (S-V-4), -   R³⁰=cyclopropyl, R³¹═R³³=H, R³⁴=2-Me (S-V-5), -   R³⁰=tert-butyl, R³¹═R³³=H, R³⁴=2-OMe (S-V-6).

Preference is furthermore given to safeners of the formula (S-VI) in which

-   X³ is CH; -   R³⁵ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₂-C₆)-alkenyl,     (C₅-C₆)-cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl having     up to three heteroatoms from the group consisting of nitrogen,     oxygen and sulfur, where the six last-mentioned radicals are     optionally substituted by one or more identical or different     substituents from the group consisting of halogen, (C₁-C₆)-alkoxy,     (C₁-C₆)-haloalkoxy, (C₁-C₂)-alkylsulfinyl, (C₁-C₂)-alkylsulfonyl,     (C₃-C₆)-cycloalkyl, (C₁-C₄)-alkoxycarbonyl, (C₁-C₄)-alkylcarbonyl     and phenyl and, in the case of cyclic radicals, also (C₁-C₄)-alkyl     and (C₁-C₄)-haloalkyl; -   R³⁶ is hydrogen, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl,     where the three last-mentioned radicals are optionally substituted     by one or more identical or different substituents from the group     consisting of halogen, hydroxyl, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and     (C₁-C₄)-alkylthio; -   R³⁷ is halogen, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy, nitro,     (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylsulfonyl,     (C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylcarbonyl; -   R³⁸ is hydrogen; -   R³⁹ is halogen, nitro, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,     (C₁-C₄)-haloalkoxy, (C₃-C₆)-cycloalkyl, phenyl, (C₁-C₄)-alkoxy,     cyano, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl,     (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkoxycarbonyl or     (C₁-C₄)-alkylcarbonyl; -   n is 0, 1 or 2 and -   m is 1 or 2.

Preferred safeners of the formula (S-VII) are (S-3-1), (S-3-2), (S-3-3), (S-3-4) and (S-3-5).

Preferred safeners of the formula (VIII) are

-   1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea (S-VIII-1), -   1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea     (S-VIII-2), -   1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea (S-VIII-3)     and -   1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea (S-VIII-4),

Preferred safeners of the formula S-IX are compounds of the formulae S-IX-A1 to S-IX-A4,

from among which the compound S-IX-A3 is very particularly preferred as safener.

Particularly preferred combinations of herbicidally active compounds of the formula (I) as listed in any of Tables 1 to 4 and safeners (B) are those in which the safener (B) is selected from the group of safeners consisting of the compounds of the formulae S-II-1 (mefenpyr-diethyl), S-II-9 (isoxadifen-ethyl), S-III-1 (chloquintocet-mexyl), S-b-11 (fenclorim), S-b-14 (dymron), S-IX-A3 (4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzenesulfonamide [N-({4-[(cyclopropylamino)carbonyl]phenyl}-sulfonyl)-2-methoxybenzamide], very particularly preferred as safeners (B) are the compounds S-II-1 and S-IX-A3).

Particularly preferred for use in rice is isoxadifen-ethyl. Particularly preferred for use in cereals are mefenpyr-diethyl, cloquintocet-mexyl and 4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)benzenesulfonamide [N-({4-[(cyclopropylamino)carbonyl]phenyl}sulfonyl)-2-methoxybenzamide], in corn in particular isoxadifen-ethyl and 4-cyclopropylaminocarbonyl-N-(2-methoxybenzoyl)-benzenesulfonamide [N-({4-[(cyclopropylamino)carbonyl]phenyl}sulfonyl)-2-methoxybenzamide]. For use in sugar cane, preference is given to isoxadifen-ethyl. A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, is also possible.

Some of the safeners are already known as herbicides and accordingly, in addition to the herbicidal action against harmful plants, also act by protecting the crop plants.

The weight ratios of herbicide (mixture) to safener generally depend on the herbicide application rate and the effectiveness of the safener in question and may vary within wide limits, for example in the range from 200:1 to 1:200, preferably from 100:1 to 1:100, in particular from 20:1 to 1:20. The safeners may be formulated analogously to the compounds of the formula (I) or their mixtures with other herbicides/pesticides and be provided and used as a finished formulation or as a tank mix with the herbicides.

For application, the formulations present in commercial form are, if appropriate, diluted in a customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules with water. Preparations in the form of dusts, granules for soil application or granules for broadcasting and sprayable solutions are usually not diluted with other inert substances prior to application.

The application rate of the compounds of the formula (I) varies according to the external conditions such as, inter alia, temperature, humidity and the type of herbicide used. It may vary within wide limits, for example between 0.001 and 10.0 kg/ha or more of active substance; however, preferably it is between 0.005 and 5 kg/ha.

The present invention is illustrated in more detail by the examples below; however, these examples do not limit the invention in any way.

A. SYNTHESIS EXAMPLES

Some examples of syntheses of compounds of the formula (I) or salts thereof are described in an exemplary manner below.

5-Bromo-2-[(S)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Ex. 2637) and 5-bromo-2-[(R)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Ex. 3725)

The starting material [5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl imidothiocarbamate hydrobromide is obtained by mixing equimolar amounts of 4-(bromomethyl)-5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazole and thiourea in ethanol and heating under reflux for 8 hours, concentrating the resulting mixture and recrystallizing from tetrahydrofuran.

[5-(Difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl imidothiocarbamate hydrobromide (7.928 g, 21 mmol) is added to a mixture, stirred vigorously, of 100 ml of toluene and 50% strength aqueous sodium hydroxide solution (50 g), and the mixture is stirred vigorously for another 1.5 hours. Tetra-n-butylammonium bromide (1.858 g, 6 mmol) and 2,5-dibromo-1,3-thiazole (5.0 g, 21 mmol) are then added, and the mixture is stirred at 25° C. for a further 5 hours and then allowed to stand overnight. For work-up, the reaction solution is added to water and extracted with toluene. The combined organic phases are dried and concentrated. For purification, the product is chromatographed on silica gel (heptane/ethyl acetate, gradient). This gives 5.62 g of product (61.1% of theory).

NMR (CDCl₃, 400 MHz): 3.8 (s, 3H, CH₃); 4.31 (s, 2H, SCH₂); 6.69 (t, 1H, OCHF₂); 7.58 (s, 1H, thiazolyl-H).

The 5-bromo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfanyl)-1,3-thiazole obtained in this manner (4.0 g, 9.429 mmol) is initially charged in 100 ml of toluene. With stirring, 3-chloroperbenzoic acid (1.976 g, 8.015 mmol, 77% pure) is then added a little at a time, and the mixture is stirred at room temperature for a further 4 hours. For work-up, the reaction mixture is washed successively with water, aqueous NaHSO₃ solution, aqueous NaHCO₃ solution and finally with NaCl solution. The organic phase is dried over magnesium sulfate, filtered off and concentrated. The residue is triturated with n-heptane, filtered off and dried. The racemic 5-bromo-2-({[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl)-1,3-thiazole obtained (3.75 g) is purified by preparative chiral HPLC (column: Chiralcel® OD; mobile phase: n-hexane/2-propanol 90:10; flow rate: 0.6 ml/min; column temperature: 25° C.) and separated into the enantiomers. This gives 1.505 g (36.2% of theory) of 5-bromo-2-[(S)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (R_(t)=10.258 min) and 1.305 g (31.4% of theory) of 5-bromo-2-[(R)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (R_(t)=12.557 min).

The absolute configuration of 5-bromo-2-[(S)-{[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole was confirmed by X-ray analysis.

5-Bromo-2-[(S)-{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Ex. 2632) and 5-bromo-2-[(R)-{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (Ex. 3720)

Molecular sieve 4 A (0.610 g) is initially charged in dichloromethane (5 ml). The catalyst titanium(IV) isopropoxide (0.18 ml, 0.62 mmol) and the ligand (R)-(−)-mandelic acid (0.142 g, 0.93 mmol) are added. The mixture is stirred at room temperature for a further 30 minutes. 5-Bromo-2-({[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}-sulfanyl)-1,3-thiazole, which can be obtained according to WO 2006/123088, is then added (0.610 g, 1.55 mmol). The mixture is stirred at room temperature for a further hour, during which time the catalyst/ligand complex forms. Cumene hydroperoxide is then added dropwise (0.29 ml, 80%, 1.55 mmol). The mixture is then stirred at room temperature for a further seven hours and stored in a fridge (−5° C.) for one week. For work-up, the reaction mixture is washed successively with water, twice with aqueous 2M NaOH solution and finally with NaCl solution. The organic phase is dried over magnesium sulfate, filtered off and concentrated. The crude product obtained contains 5-bromo-2-[{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole and the corresponding sulfone (0.3 g, about 1:1) and is purified by preparative HPLC. This gives 0.116 g (18.2% of theory) of 5-bromo-2-[{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole with 11% ee (S), which is separated into the enantiomers by preparative chiral HPLC. This gives 0.063 g (10% of theory) of 5-bromo-2-[(S)-{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (R_(t)=18.600 min) and 0.042 g (7% of theory) of 5-bromo-2-[(R)-{[5-chloro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfinyl]-1,3-thiazole (R_(t)=22.652 min).

5-Bromo-2-[(S)-(2,6-difluorobenzyl)sulfinyl]-1,3-thiazole (Ex. 259) and 5-bromo-2-[(R)-(2,6-difluorobenzyl)sulfinyl]-1,3-thiazole (Ex. 1449)

a) Preparation of 5-bromo-2-[(2,6-difluorobenzyl)sulfanyl]-1,3-thiazole

The starting material 2,6-difluorobenzyl imidothiocarbamate hydrochloride is obtained by mixing equimolar amounts of 2,6-difluorobenzyl chloride and thiourea in ethanol, heating under reflux for 8 hours, concentrating and recrystallizing from tetrahydrofuran.

2,6-Difluorobenzyl imidothiocarbamate hydrochloride (1.972 g, 8 mmol) is added to a vigorously stirred mixture consisting of 50 ml of toluene and 50% strength aqueous sodium hydroxide solution (28 g), and the mixture is stirred vigorously for a further 1.5 hours. Tetra-n-butylammonium bromide (0.746 g, 2 mmol) and 5-bromo-2-(methylsulfonyl)-1,3-thiazole (2.0 g, 8 mmol) are added, and the mixture is stirred at 25° C. for a further 6 hours and allowed to stand overnight. For work-up, the reaction solution is added to water and extracted with toluene. The combined organic phases are dried and concentrated. For purification, the product is chromatographed on silica gel (heptane/ethyl acetate, gradient). This gives 1.7 g of product (60.6% of theory).

NMR (CDCl₃, 400 MHz): 4.42 (s, 2H, SCH₂); 6.89 (m, 2H, Ar); 7.24 (m, 1H, Ar); 7.61 (s, 1H, thiazolyl-H).

b) Asymmetric Sulfoxidation

The ligand (R,R)-1,2-diphenylethane-1,2-diol [(R,R)-(+)-hydrobenzoin, 0.033 g, 0.15 mmol] is initially charged in CCl₄ (10 ml). The catalyst titanium(IV) isopropoxide (0.02 ml, 0.077 mmol) is added, and water (0.028 ml, 1.55 mmol) is then added dropwise. The mixture is stirred at room temperature for 15 minutes. 5-Bromo-2-[(2,6-difluorobenzyl)sulfanyl]-1,3-thiazole (0.5 g, 1.55 mmol) is then added, and the mixture is stirred at room temperature for a further 15 minutes. With ice-bath cooling, tert-butyl hydroperoxide (TBHP, 70% strength in water, 0.44 ml, 3 mmol) is then added dropwise. The mixture is stirred for a further two hours and then allowed to thaw overnight. For work-up, the reaction mixture is diluted with dichloromethane and washed successively with water, twice with 5% strength Na₂S₂O₅ solution and finally with NaCl solution. The organic phase is dried over magnesium sulfate, filtered off and concentrated. The residue is chromatographed on silica gel (heptane/ethyl acetate 10:0 to 7:3). The mixture obtained (0.120 g) comprises 5-bromo-2-[(S)-(2,6-difluorobenzyl)sulfinyl]-1,3-thiazole with 23% ee (S) and the corresponding sulfone and is directly separated into the enantiomers by preparative chiral HPLC. This gives 0.032 g (6% of theory) of 5-bromo-2-[(S)-(2,6-difluorobenzyl)sulfinyl]-1,3-thiazole (R_(t)=17.053 min) and 0.032 g (6% of theory) of 5-bromo-2-[(R)-(2,6-difluorobenzyl)sulfinyl]-1,3-thiazole (R_(t)=19.430 min).

Retention times (R_(t), in minutes) and enantiomeric excess (ee) of chiral compounds are determined by analytic chiral HPLC [Chiralcel® OD column (250×4.6 mm, particle size 5 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v].

The racemates or enantiomeric mixtures are separated into the respective enantiomers by preparative chiral HPLC [Chiralcel® OD column (250×5 mm, particle size 10 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v].

The compounds described in Tables 1-4 below are obtained according to or analogously to the synthesis examples described above.

In the tables:

-   Me=methyl -   Et=ethyl -   Ph=phenyl -   Pr=n-propyl -   cPr=cyclopropyl -   ^(i)Pr=isopropyl -   Bu=n-butyl -   cBu=cyclobutyl -   iBu=isobutyl -   sBu=sec-butyl -   ^(t)Bu=tert-butyl -   cPen=cyclopentyl -   cHex=cyclohexyl

TABLE 1 Compounds of the formula Ia-S (Ia-S)

Ex. No. R¹¹ R¹² R¹ R² R³ R⁴ R⁵ 1. H H H H H H H 2. H H F H H H H 3. H H F H H F H 4. H H F H H H F 5. H H F Me H H F 6. H H F H H H Cl 7. H H CF₃ H H H H 8. H H Me H H H H 9. H H F H H H CF₃ 10. H H F CF₃ H H F 11. H H Br H H H H 12. H H I H H H H 13. H H Cl H H H H 14. H H Cl H Cl H H 15. H H Cl H H H Cl 16. H H H Cl Cl H H 17. H H Cl Cl Cl H H 18. H H Cl Cl H Cl H 19. H H Cl Cl Cl H Cl 20. H H Cl Cl Cl Cl H 21. H H Cl Cl Cl Cl Cl 22. H H Cl Cl H H Cl 23. H H Cl H Cl Cl H 24. H H Cl H H Cl Cl 25. H H H Cl Cl Cl H 26. H H NO₂ H H H H 27. H H H Cl H H H 28. H H H H Cl H H 29. H H Cl H Cl H Cl 30. H H Cl Cl H H H 31. H H Cl H H Cl H 32. H H H Cl H Cl H 33. H H H OMe H H H 34. H H C(O)OMe H H H H 35. H H F Cl H H H 36. H H F Me H H H 37. H H H Me H H H 38. H H OMe H H H H 39. H H F F F H H 40. H H F F H F H 41. H H H F F F H 42. H H F H F F H 43. H H Me H Me H H 44. H H Me H H Me H 45. H H F H H CF₃ H 46. H H F H Br H H 47. H H Me Me H H H 48. H H F F F F F 49. H H F H H H OMe 50. H H Cl H F H H 51. H H NO₂ H Cl H H 52. H H NO₂ H H Me H 53. H H F H H H I 54. H H F H H H Br 55. H H Br H H H Br 56. H H Cl H H H Me 57. H H Cl H H H OCHF₂ 58. H H Cl H H H OMe 59. H H Me H H H OMe 60. H H OEt H H H CF₃ 61. H H OC(O)Me H H H H 62. H H OEt H H H Me 63. H H Me Me H H Me 64. H H Cl H H H C(O)OMe 65. H H Cl H H OMe H 66. H H F F H F F 67. H H Cl H H F H 68. H H F H H F Cl 69. H H F H H Cl H 70. H H Cl H H CF₃ H 71. H H Cl Me H H H 72. H H OCHF₂ H H H H 73. H H OCH₂CF₃ H H H H 74. H H CF₃ H H H OCHF₂ 75. H H CF₃ H H H OCH₂CF₃ 76. H H Me H H H Me 77. H H Cl H H H F 78. H H F H F H H 79. H H F Me H H Cl 80. H H F H H OMe H 81. H H Cl H OCH₂O H 82. H H Me H H F H 83. H H OCF₃ H H H H 84. H H F F H H H 85. H H OMe H H Cl H 86. F H H H H H H 87. F H F H H H H 88. F H F H H F H 89. F H F H H H F 90. F H F Me H H F 91. F H F H H H Cl 92. F H CF₃ H H H H 93. F H Me H H H H 94. F H F H H H CF₃ 95. F H F CF₃ H H F 96. F H Br H H H H 97. F H I H H H H 98. F H Cl H H H H 99. F H Cl H Cl H H 100. F H Cl H H H Cl 101. F H H Cl Cl H H 102. F H Cl Cl Cl H H 103. F H Cl Cl H Cl H 104. F H Cl Cl Cl H Cl 105. F H Cl Cl Cl Cl H 106. F H Cl Cl Cl Cl Cl 107. F H Cl Cl H H Cl 108. F H Cl H Cl Cl H 109. F H Cl H H Cl Cl 110. F H H Cl Cl Cl H 111. F H NO₂ H H H H 112. F H H Cl H H H 113. F H H H Cl H H 114. F H Cl H Cl H Cl 115. F H Cl Cl H H H 116. F H Cl H H Cl H 117. F H H Cl H Cl H 118. F H H OMe H H H 119. F H C(O)OMe H H H H 120. F H F Cl H H H 121. F H F Me H H H 122. F H H Me H H H 123. F H OMe H H H H 124. F H F F F H H 125. F H F F H F H 126. F H H F F F H 127. F H F H F F H 128. F H Me H Me H H 129. F H Me H H Me H 130. F H F H H CF₃ H 131. F H F H Br H H 132. F H Me Me H H H 133. F H F F F F F 134. F H F H H H OMe 135. F H Cl H F H H 136. F H NO₂ H Cl H H 137. F H NO₂ H H Me H 138. F H F H H H I 139. F H F H H H Br 140. F H Br H H H Br 141. F H Cl H H H Me 142. F H Cl H H H OCHF₂ 143. F H Cl H H H OMe 144. F H Me H H H OMe 145. F H OEt H H H CF₃ 146. F H OC(O)Me H H H H 147. F H OEt H H H Me 148. F H Me Me H H Me 149. F H Cl H H H C(O)OMe 150. F H Cl H H OMe H 151. F H F F H F F 152. F H Cl H H F H 153. F H F H H F Cl 154. F H F H H Cl H 155. F H Cl H H CF₃ H 156. F H Cl Me H H H 157. F H OCHF₂ H H H H 158. F H OCH₂CF₃ H H H H 159. F H CF₃ H H H OCHF₂ 160. F H CF₃ H H H OCH₂CF₃ 161. F H Me H H H Me 162. F H Cl H H H F 163. F H F H F H H 164. F H F Me H H Cl 165. F H F H H OMe H 166. F H Cl H OCH₂O H 167. F H Me H H F H 168. F H OCF₃ H H H H 169. F H F F H H H 170. F H OMe H H Cl H 171. Cl H H H H H H 172. Cl H F H H H H 173. Cl H F H H F H 174. Cl H F H H H F 175. Cl H F Me H H F 176. Cl H F H H H Cl 177. Cl H CF₃ H H H H 178. Cl H Me H H H H 179. Cl H F H H H CF₃ 180. Cl H F CF₃ H H F 181. Cl H Br H H H H 182. Cl H I H H H H 183. Cl H Cl H H H H 184. Cl H Cl H Cl H H 185. Cl H Cl H H H Cl 186. Cl H H Cl Cl H H 187. Cl H Cl Cl Cl H H 188. Cl H Cl Cl H Cl H 189. Cl H Cl Cl Cl H Cl 190. Cl H Cl Cl Cl Cl H 191. Cl H Cl Cl Cl Cl Cl 192. Cl H Cl Cl H H Cl 193. Cl H Cl H Cl Cl H 194. Cl H Cl H H Cl Cl 195. Cl H H Cl Cl Cl H 196. Cl H NO₂ H H H H 197. Cl H H Cl H H H 198. Cl H H H Cl H H 199. Cl H Cl H Cl H Cl 200. Cl H Cl Cl H H H 201. Cl H Cl H H Cl H 202. Cl H H Cl H Cl H 203. Cl H H OMe H H H 204. Cl H C(O)OMe H H H H 205. Cl H F Cl H H H 206. Cl H F Me H H H 207. Cl H H Me H H H 208. Cl H OMe H H H H 209. Cl H F F F H H 210. Cl H F F H F H 211. Cl H H F F F H 212. Cl H F H F F H 213. Cl H Me H Me H H 214. Cl H Me H H Me H 215. Cl H F H H CF₃ H 216. Cl H F H Br H H 217. Cl H Me Me H H H 218. Cl H F F F F F 219. Cl H F H H H OMe 220. Cl H Cl H F H H 221. Cl H NO₂ H Cl H H 222. Cl H NO₂ H H Me H 223. Cl H F H H H I 224. Cl H F H H H Br 225. Cl H Br H H H Br 226. Cl H Cl H H H Me 227. Cl H Cl H H H OCHF₂ 228. Cl H Cl H H H OMe 229. Cl H Me H H H OMe 230. Cl H OEt H H H CF₃ 231. Cl H OC(O)Me H H H H 232. Cl H OEt H H H Me 233. Cl H Me Me H H Me 234. Cl H Cl H H H C(O)OMe 235. Cl H Cl H H OMe H 236. Cl H F F H F F 237. Cl H Cl H H F H 238. Cl H F H H F Cl 239. Cl H F H H Cl H 240. Cl H Cl H H CF₃ H 241. Cl H Cl Me H H H 242. Cl H OCHF₂ H H H H 243. Cl H OCH₂CF₃ H H H H 244. Cl H CF₃ H H H OCHF₂ 245. Cl H CF₃ H H H OCH₂CF₃ 246. Cl H Me H H H Me 247. Cl H Cl H H H F 248. Cl H F H F H H 249. Cl H F Me H H Cl 250. Cl H F H H OMe H 251. Cl H Cl H OCH₂O H 252. Cl H Me H H F H 253. Cl H OCF₃ H H H H 254. Cl H F F H H H 255. Cl H OMe H H Cl H 256. Br H H H H H H 257. Br H F H H H H 258. Br H F H H F H 259. Br H F H H H F 260. Br H F Me H H F 261. Br H F H H H Cl 262. Br H CF₃ H H H H 263. Br H Me H H H H 264. Br H F H H H CF₃ 265. Br H F CF₃ H H F 266. Br H Br H H H H 267. Br H I H H H H 268. Br H Cl H H H H 269. Br H Cl H Cl H H 270. Br H Cl H H H Cl 271. Br H H Cl Cl H H 272. Br H Cl Cl Cl H H 273. Br H Cl Cl H Cl H 274. Br H Cl Cl Cl H Cl 275. Br H Cl Cl Cl Cl H 276. Br H Cl Cl Cl Cl Cl 277. Br H Cl Cl H H Cl 278. Br H Cl H Cl Cl H 279. Br H Cl H H Cl Cl 280. Br H H Cl Cl Cl H 281. Br H NO₂ H H H H 282. Br H H Cl H H H 283. Br H H H Cl H H 284. Br H Cl H Cl H Cl 285. Br H Cl Cl H H H 286. Br H Cl H H Cl H 287. Br H H Cl H Cl H 288. Br H H OMe H H H 289. Br H C(O)OMe H H H H 290. Br H F Cl H H H 291. Br H F Me H H H 292. Br H H Me H H H 293. Br H OMe H H H H 294. Br H F F F H H 295. Br H F F H F H 296. Br H H F F F H 297. Br H F H F F H 298. Br H Me H Me H H 299. Br H Me H H Me H 300. Br H F H H CF₃ H 301. Br H F H Br H H 302. Br H Me Me H H H 303. Br H F F F F F 304. Br H F H H H OMe 305. Br H Cl H F H H 306. Br H NO₂ H Cl H H 307. Br H NO₂ H H Me H 308. Br H F H H H I 309. Br H F H H H Br 310. Br H Br H H H Br 311. Br H Cl H H H Me 312. Br H Cl H H H OCHF₂ 313. Br H Cl H H H OMe 314. Br H Me H H H OMe 315. Br H OEt H H H CF₃ 316. Br H OC(O)Me H H H H 317. Br H OEt H H H Me 318. Br H Me Me H H Me 319. Br H Cl H H H C(O)OMe 320. Br H Cl H H OMe H 321. Br H F F H F F 322. Br H Cl H H F H 323. Br H F H H F Cl 324. Br H F H H Cl H 325. Br H Cl H H CF₃ H 326. Br H Cl Me H H H 327. Br H OCHF₂ H H H H 328. Br H OCH₂CF₃ H H H H 329. Br H CF₃ H H H OCHF₂ 330. Br H CF₃ H H H OCH₂CF₃ 331. Br H Me H H H Me 332. Br H Cl H H H F 333. Br H F H F H H 334. Br H F Me H H Cl 335. Br H F H H OMe H 336. Br H Cl H OCH₂O H 337. Br H Me H H F H 338. Br H OCF₃ H H H H 339. Br H F F H H H 340. Br H OMe H H Cl H 341. I H H H H H H 342. I H F H H H H 343. I H F H H F H 344. I H F H H H F 345. I H F Me H H F 346. I H F H H H Cl 347. I H CF₃ H H H H 348. I H Me H H H H 349. I H F H H H CF₃ 350. I H F CF₃ H H F 351. I H Br H H H H 352. I H I H H H H 353. I H Cl H H H H 354. I H Cl H Cl H H 355. I H Cl H H H Cl 356. I H H Cl Cl H H 357. I H Cl Cl Cl H H 358. I H Cl Cl H Cl H 359. I H Cl Cl Cl H Cl 360. I H Cl Cl Cl Cl H 361. I H Cl Cl Cl Cl Cl 362. I H Cl Cl H H Cl 363. I H Cl H Cl Cl H 364. I H Cl H H Cl Cl 365. I H H Cl Cl Cl H 366. I H NO₂ H H H H 367. I H H Cl H H H 368. I H H H Cl H H 369. I H Cl H Cl H Cl 370. I H Cl Cl H H H 371. I H Cl H H Cl H 372. I H H Cl H Cl H 373. I H H OMe H H H 374. I H C(O)OMe H H H H 375. I H F Cl H H H 376. I H F Me H H H 377. I H H Me H H H 378. I H OMe H H H H 379. I H F F F H H 380. I H F F H F H 381. I H H F F F H 382. I H F H F F H 383. I H Me H Me H H 384. I H Me H H Me H 385. I H F H H CF₃ H 386. I H F H Br H H 387. I H Me Me H H H 388. I H F F F F F 389. I H F H H H OMe 390. I H Cl H F H H 391. I H NO₂ H Cl H H 392. I H NO₂ H H Me H 393. I H F H H H I 394. I H F H H H Br 395. I H Br H H H Br 396. I H Cl H H H Me 397. I H Cl H H H OCHF₂ 398. I H Cl H H H OMe 399. I H Me H H H OMe 400. I H OEt H H H CF₃ 401. I H OC(O)Me H H H H 402. I H OEt H H H Me 403. I H Me Me H H Me 404. I H Cl H H H C(O)OMe 405. I H Cl H H OMe H 406. I H F F H F F 407. I H Cl H H F H 408. I H F H H F Cl 409. I H F H H Cl H 410. I H Cl H H CF₃ H 411. I H Cl Me H H H 412. I H OCHF₂ H H H H 413. I H OCH₂CF₃ H H H H 414. I H CF₃ H H H OCHF₂ 415. I H CF₃ H H H OCH₂CF₃ 416. I H Me H H H Me 417. I H Cl H H H F 418. I H F H F H H 419. I H F Me H H Cl 420. I H F H H OMe H 421. I H Cl H OCH₂O H 422. I H Me H H F H 423. I H OCF₃ H H H H 424. I H F F H H H 425. I H OMe H H Cl H 426. H Cl H H H H H 427. H Cl F H H H H 428. H Cl F H H F H 429. H Cl F H H H F 430. H Cl F Me H H F 431. H Cl F H H H Cl 432. H Cl CF₃ H H H H 433. H Cl Me H H H H 434. H Cl F H H H CF₃ 435. H Cl F CF₃ H H F 436. H Cl Br H H H H 437. H Cl I H H H H 438. H Cl Cl H H H H 439. H Cl Cl H Cl H H 440. H Cl Cl H H H Cl 441. H Cl H Cl Cl H H 442. H Cl Cl Cl Cl H H 443. H Cl Cl Cl H Cl H 444. H Cl Cl Cl Cl H Cl 445. H Cl Cl Cl Cl Cl H 446. H Cl Cl Cl Cl Cl Cl 447. H Cl Cl Cl H H Cl 448. H Cl Cl H Cl Cl H 449. H Cl Cl H H Cl Cl 450. H Cl H Cl Cl Cl H 451. H Cl NO₂ H H H H 452. H Cl H Cl H H H 453. H Cl H H Cl H H 454. H Cl Cl H Cl H Cl 455. H Cl Cl Cl H H H 456. H Cl Cl H H Cl H 457. H Cl H Cl H Cl H 458. H Cl H OMe H H H 459. H Cl C(O)OMe H H H H 460. H Cl F Cl H H H 461. H Cl F Me H H H 462. H Cl H Me H H H 463. H Cl OMe H H H H 464. H Cl F F F H H 465. H Cl F F H F H 466. H Cl H F F F H 467. H Cl F H F F H 468. H Cl Me H Me H H 469. H Cl Me H H Me H 470. H Cl F H H CF₃ H 471. H Cl F H Br H H 472. H Cl Me Me H H H 473. H Cl F F F F F 474. H Cl F H H H OMe 475. H Cl Cl H F H H 476. H Cl NO₂ H Cl H H 477. H Cl NO₂ H H Me H 478. H Cl F H H H I 479. H Cl F H H H Br 480. H Cl Br H H H Br 481. H Cl Cl H H H Me 482. H Cl Cl H H H OCHF₂ 483. H Cl Cl H H H OMe 484. H Cl Me H H H OMe 485. H Cl OEt H H H CF₃ 486. H Cl OC(O)Me H H H H 487. H Cl OEt H H H Me 488. H Cl Me Me H H Me 489. H Cl Cl H H H C(O)OMe 490. H Cl Cl H H OMe H 491. H Cl F F H F F 492. H Cl Cl H H F H 493. H Cl F H H F Cl 494. H Cl F H H Cl H 495. H Cl Cl H H CF₃ H 496. H Cl Cl Me H H H 497. H Cl OCHF₂ H H H H 498. H Cl OCH₂CF₃ H H H H 499. H Cl CF₃ H H H OCHF₂ 500. H Cl CF₃ H H H OCH₂CF₃ 501. H Cl Me H H H Me 502. H Cl Cl H H H F 503. H Cl F H F H H 504. H Cl F Me H H Cl 505. H Cl F H H OMe H 506. H Cl Cl H OCH₂O H 507. H Cl Me H H F H 508. H Cl OCF₃ H H H H 509. H Cl F F H H H 510. H Cl OMe H H Cl H 511. H Br H H H H H 512. H Br F H H H H 513. H Br F H H F H 514. H Br F H H H F 515. H Br F Me H H F 516. H Br F H H H Cl 517. H Br CF₃ H H H H 518. H Br Me H H H H 519. H Br F H H H CF₃ 520. H Br F CF₃ H H F 521. H Br Br H H H H 522. H Br I H H H H 523. H Br Cl H H H H 524. H Br Cl H Cl H H 525. H Br Cl H H H Cl 526. H Br H Cl Cl H H 527. H Br Cl Cl Cl H H 528. H Br Cl Cl H Cl H 529. H Br Cl Cl Cl H Cl 530. H Br Cl Cl Cl Cl H 531. H Br Cl Cl Cl Cl Cl 532. H Br Cl Cl H H Cl 533. H Br Cl H Cl Cl H 534. H Br Cl H H Cl Cl 535. H Br H Cl Cl Cl H 536. H Br NO₂ H H H H 537. H Br H Cl H H H 538. H Br H H Cl H H 539. H Br Cl H Cl H Cl 540. H Br Cl Cl H H H 541. H Br Cl H H Cl H 542. H Br H Cl H Cl H 543. H Br H OMe H H H 544. H Br C(O)OMe H H H H 545. H Br F Cl H H H 546. H Br F Me H H H 547. H Br H Me H H H 548. H Br OMe H H H H 549. H Br F F F H H 550. H Br F F H F H 551. H Br H F F F H 552. H Br F H F F H 553. H Br Me H Me H H 554. H Br Me H H Me H 555. H Br F H H CF₃ H 556. H Br F H Br H H 557. H Br Me Me H H H 558. H Br F F F F F 559. H Br F H H H OMe 560. H Br Cl H F H H 561. H Br NO₂ H Cl H H 562. H Br NO₂ H H Me H 563. H Br F H H H I 564. H Br F H H H Br 565. H Br Br H H H Br 566. H Br Cl H H H Me 567. H Br Cl H H H OCHF₂ 568. H Br Cl H H H OMe 569. H Br Me H H H OMe 570. H Br OEt H H H CF₃ 571. H Br OC(O)Me H H H H 572. H Br OEt H H H Me 573. H Br Me Me H H Me 574. H Br Cl H H H C(O)OMe 575. H Br Cl H H OMe H 576. H Br F F H F F 577. H Br Cl H H F H 578. H Br F H H F Cl 579. H Br F H H Cl H 580. H Br Cl H H CF₃ H 581. H Br Cl Me H H H 582. H Br OCHF₂ H H H H 583. H Br OCH₂CF₃ H H H H 584. H Br CF₃ H H H OCHF₂ 585. H Br CF₃ H H H OCH₂CF₃ 586. H Br Me H H H Me 587. H Br Cl H H H F 588. H Br F H F H H 589. H Br F Me H H Cl 590. H Br F H H OMe H 591. H Br Cl H OCH₂O H 592. H Br Me H H F H 593. H Br OCF₃ H H H H 594. H Br F F H H H 595. H Br OMe H H Cl H 596. Me H H H H H H 597. Me H F H H H H 598. Me H F H H F H 599. Me H F H H H F 600. Me H F Me H H F 601. Me H F H H H Cl 602. Me H CF₃ H H H H 603. Me H Me H H H H 604. Me H F H H H CF₃ 605. Me H F CF₃ H H F 606. Me H Br H H H H 607. Me H I H H H H 608. Me H Cl H H H H 609. Me H Cl H Cl H H 610. Me H Cl H H H Cl 611. Me H H Cl Cl H H 612. Me H Cl Cl Cl H H 613. Me H Cl Cl H Cl H 614. Me H Cl Cl Cl H Cl 615. Me H Cl Cl Cl Cl H 616. Me H Cl Cl Cl Cl Cl 617. Me H Cl Cl H H Cl 618. Me H Cl H Cl Cl H 619. Me H Cl H H Cl Cl 620. Me H H Cl Cl Cl H 621. Me H NO₂ H H H H 622. Me H H Cl H H H 623. Me H H H Cl H H 624. Me H Cl H Cl H Cl 625. Me H Cl Cl H H H 626. Me H Cl H H Cl H 627. Me H H Cl H Cl H 628. Me H H OMe H H H 629. Me H C(O)OMe H H H H 630. Me H F Cl H H H 631. Me H F Me H H H 632. Me H H Me H H H 633. Me H OMe H H H H 634. Me H F F F H H 635. Me H F F H F H 636. Me H H F F F H 637. Me H F H F F H 638. Me H Me H Me H H 639. Me H Me H H Me H 640. Me H F H H CF₃ H 641. Me H F H Br H H 642. Me H Me Me H H H 643. Me H F F F F F 644. Me H F H H H OMe 645. Me H Cl H F H H 646. Me H NO₂ H Cl H H 647. Me H NO₂ H H Me H 648. Me H F H H H I 649. Me H F H H H Br 650. Me H Br H H H Br 651. Me H Cl H H H Me 652. Me H Cl H H H OCHF₂ 653. Me H Cl H H H OMe 654. Me H Me H H H OMe 655. Me H OEt H H H CF₃ 656. Me H OC(O)Me H H H H 657. Me H OEt H H H Me 658. Me H Me Me H H Me 659. Me H Cl H H H C(O)OMe 660. Me H Cl H H OMe H 661. Me H F F H F F 662. Me H Cl H H F H 663. Me H F H H F Cl 664. Me H F H H Cl H 665. Me H Cl H H CF₃ H 666. Me H Cl Me H H H 667. Me H OCHF₂ H H H H 668. Me H OCH₂CF₃ H H H H 669. Me H CF₃ H H H OCHF₂ 670. Me H CF₃ H H H OCH₂CF₃ 671. Me H Me H H H Me 672. Me H Cl H H H F 673. Me H F H F H H 674. Me H F Me H H Cl 675. Me H F H H OMe H 676. Me H Cl H OCH₂O H 677. Me H Me H H F H 678. Me H OCF₃ H H H H 679. Me H F F H H H 680. Me H OMe H H Cl H 681. H Me H H H H H 682. H Me F H H H H 683. H Me F H H F H 684. H Me F H H H F 685. H Me F Me H H F 686. H Me F H H H Cl 687. H Me CF₃ H H H H 688. H Me Me H H H H 689. H Me F H H H CF₃ 690. H Me F CF₃ H H F 691. H Me Br H H H H 692. H Me I H H H H 693. H Me Cl H H H H 694. H Me Cl H Cl H H 695. H Me Cl H H H Cl 696. H Me H Cl Cl H H 697. H Me Cl Cl Cl H H 698. H Me Cl Cl H Cl H 699. H Me Cl Cl Cl H Cl 700. H Me Cl Cl Cl Cl H 701. H Me Cl Cl Cl Cl Cl 702. H Me Cl Cl H H Cl 703. H Me Cl H Cl Cl H 704. H Me Cl H H Cl Cl 705. H Me H Cl Cl Cl H 706. H Me NO₂ H H H H 707. H Me H Cl H H H 708. H Me H H Cl H H 709. H Me Cl H Cl H Cl 710. H Me Cl Cl H H H 711. H Me Cl H H Cl H 712. H Me H Cl H Cl H 713. H Me H OMe H H H 714. H Me C(O)OMe H H H H 715. H Me F Cl H H H 716. H Me F Me H H H 717. H Me H Me H H H 718. H Me OMe H H H H 719. H Me F F F H H 720. H Me F F H F H 721. H Me H F F F H 722. H Me F H F F H 723. H Me Me H Me H H 724. H Me Me H H Me H 725. H Me F H H CF₃ H 726. H Me F H Br H H 727. H Me Me Me H H H 728. H Me F F F F F 729. H Me F H H H OMe 730. H Me Cl H F H H 731. H Me NO₂ H Cl H H 732. H Me NO₂ H H Me H 733. H Me F H H H I 734. H Me F H H H Br 735. H Me Br H H H Br 736. H Me Cl H H H Me 737. H Me Cl H H H OCHF₂ 738. H Me Cl H H H OMe 739. H Me Me H H H OMe 740. H Me OEt H H H CF₃ 741. H Me OC(O)Me H H H H 742. H Me OEt H H H Me 743. H Me Me Me H H Me 744. H Me Cl H H H C(O)OMe 745. H Me Cl H H OMe H 746. H Me F F H F F 747. H Me Cl H H F H 748. H Me F H H F Cl 749. H Me F H H Cl H 750. H Me Cl H H CF₃ H 751. H Me Cl Me H H H 752. H Me OCHF₂ H H H H 753. H Me OCH₂CF₃ H H H H 754. H Me CF₃ H H H OCHF₂ 755. H Me CF₃ H H H OCH₂CF₃ 756. H Me Me H H H Me 757. H Me Cl H H H F 758. H Me F H F H H 759. H Me F Me H H Cl 760. H Me F H H OMe H 761. H Me Cl H OCH₂O H 762. H Me Me H H F H 763. H Me OCF₃ H H H H 764. H Me F F H H H 765. H Me OMe H H Cl H 766. NO₂ H H H H H H 767. NO₂ H F H H H H 768. NO₂ H F H H F H 769. NO₂ H F H H H F 770. NO₂ H F Me H H F 771. NO₂ H F H H H Cl 772. NO₂ H CF₃ H H H H 773. NO₂ H Me H H H H 774. NO₂ H F H H H CF₃ 775. NO₂ H F CF₃ H H F 776. NO₂ H Br H H H H 777. NO₂ H I H H H H 778. NO₂ H Cl H H H H 779. NO₂ H Cl H Cl H H 780. NO₂ H Cl H H H Cl 781. NO₂ H H Cl Cl H H 782. NO₂ H Cl Cl Cl H H 783. NO₂ H Cl Cl H Cl H 784. NO₂ H Cl Cl Cl H Cl 785. NO₂ H Cl Cl Cl Cl H 786. NO₂ H Cl Cl Cl Cl Cl 787. NO₂ H Cl Cl H H Cl 788. NO₂ H Cl H Cl Cl H 789. NO₂ H Cl H H Cl Cl 790. NO₂ H H Cl Cl Cl H 791. NO₂ H NO₂ H H H H 792. NO₂ H H Cl H H H 793. NO₂ H H H Cl H H 794. NO₂ H Cl H Cl H Cl 795. NO₂ H Cl Cl H H H 796. NO₂ H Cl H H Cl H 797. NO₂ H H Cl H Cl H 798. NO₂ H H OMe H H H 799. NO₂ H C(O)OMe H H H H 800. NO₂ H F Cl H H H 801. NO₂ H F Me H H H 802. NO₂ H H Me H H H 803. NO₂ H OMe H H H H 804. NO₂ H F F F H H 805. NO₂ H F F H F H 806. NO₂ H H F F F H 807. NO₂ H F H F F H 808. NO₂ H Me H Me H H 809. NO₂ H Me H H Me H 810. NO₂ H F H H CF₃ H 811. NO₂ H F H Br H H 812. NO₂ H Me Me H H H 813. NO₂ H F F F F F 814. NO₂ H F H H H OMe 815. NO₂ H Cl H F H H 816. NO₂ H NO₂ H Cl H H 817. NO₂ H NO₂ H H Me H 818. NO₂ H F H H H I 819. NO₂ H F H H H Br 820. NO₂ H Br H H H Br 821. NO₂ H Cl H H H Me 822. NO₂ H Cl H H H OCHF₂ 823. NO₂ H Cl H H H OMe 824. NO₂ H Me H H H OMe 825. NO₂ H OEt H H H CF₃ 826. NO₂ H OC(O)Me H H H H 827. NO₂ H OEt H H H Me 828. NO₂ H Me Me H H Me 829. NO₂ H Cl H H H C(O)OMe 830. NO₂ H Cl H H OMe H 831. NO₂ H F F H F F 832. NO₂ H Cl H H F H 833. NO₂ H F H H F Cl 834. NO₂ H F H H Cl H 835. NO₂ H Cl H H CF₃ H 836. NO₂ H Cl Me H H H 837. NO₂ H OCHF₂ H H H H 838. NO₂ H OCH₂CF₃ H H H H 839. NO₂ H CF₃ H H H OCHF₂ 840. NO₂ H CF₃ H H H OCH₂CF₃ 841. NO₂ H Me H H H Me 842. NO₂ H Cl H H H F 843. NO₂ H F H F H H 844. NO₂ H F Me H H Cl 845. NO₂ H F H H OMe H 846. NO₂ H Cl H OCH₂O H 847. NO₂ H Me H H F H 848. NO₂ H OCF₃ H H H H 849. NO₂ H F F H H H 850. NO₂ H OMe H H Cl H 851. CHF₂ H H H H H H 852. CHF₂ H F H H H H 853. CHF₂ H F H H F H 854. CHF₂ H F H H H F 855. CHF₂ H F Me H H F 856. CHF₂ H F H H H Cl 857. CHF₂ H CF₃ H H H H 858. CHF₂ H Me H H H H 859. CHF₂ H F H H H CF₃ 860. CHF₂ H F CF₃ H H F 861. CHF₂ H Br H H H H 862. CHF₂ H I H H H H 863. CHF₂ H Cl H H H H 864. CHF₂ H Cl H Cl H H 865. CHF₂ H Cl H H H Cl 866. CHF₂ H H Cl Cl H H 867. CHF₂ H Cl Cl Cl H H 868. CHF₂ H Cl Cl H Cl H 869. CHF₂ H Cl Cl Cl H Cl 870. CHF₂ H Cl Cl Cl Cl H 871. CHF₂ H Cl Cl Cl Cl Cl 872. CHF₂ H Cl Cl H H Cl 873. CHF₂ H Cl H Cl Cl H 874. CHF₂ H Cl H H Cl Cl 875. CHF₂ H H Cl Cl Cl H 876. CHF₂ H NO₂ H H H H 877. CHF₂ H H Cl H H H 878. CHF₂ H H H Cl H H 879. CHF₂ H Cl H Cl H Cl 880. CHF₂ H Cl Cl H H H 881. CHF₂ H Cl H H Cl H 882. CHF₂ H H Cl H Cl H 883. CHF₂ H H OMe H H H 884. CHF₂ H C(O)OMe H H H H 885. CHF₂ H F Cl H H H 886. CHF₂ H F Me H H H 887. CHF₂ H H Me H H H 888. CHF₂ H OMe H H H H 889. CHF₂ H F F F H H 890. CHF₂ H F F H F H 891. CHF₂ H H F F F H 892. CHF₂ H F H F F H 893. CHF₂ H Me H Me H H 894. CHF₂ H Me H H Me H 895. CHF₂ H F H H CF₃ H 896. CHF₂ H F H Br H H 897. CHF₂ H Me Me H H H 898. CHF₂ H F F F F F 899. CHF₂ H F H H H OMe 900. CHF₂ H Cl H F H H 901. CHF₂ H NO₂ H Cl H H 902. CHF₂ H NO₂ H H Me H 903. CHF₂ H F H H H I 904. CHF₂ H F H H H Br 905. CHF₂ H Br H H H Br 906. CHF₂ H Cl H H H Me 907. CHF₂ H Cl H H H OCHF₂ 908. CHF₂ H Cl H H H OMe 909. CHF₂ H Me H H H OMe 910. CHF₂ H OEt H H H CF₃ 911. CHF₂ H OC(O)Me H H H H 912. CHF₂ H OEt H H H Me 913. CHF₂ H Me Me H H Me 914. CHF₂ H Cl H H H C(O)OMe 915. CHF₂ H Cl H H OMe H 916. CHF₂ H F F H F F 917. CHF₂ H Cl H H F H 918. CHF₂ H F H H F Cl 919. CHF₂ H F H H Cl H 920. CHF₂ H Cl H H CF₃ H 921. CHF₂ H Cl Me H H H 922. CHF₂ H OCHF₂ H H H H 923. CHF₂ H OCH₂CF₃ H H H H 924. CHF₂ H CF₃ H H H OCHF₂ 925. CHF₂ H CF₃ H H H OCH₂CF₃ 926. CHF₂ H Me H H H Me 927. CHF₂ H Cl H H H F 928. CHF₂ H F H F H H 929. CHF₂ H F Me H H Cl 930. CHF₂ H F H H OMe H 931. CHF₂ H Cl H OCH₂O H 932. CHF₂ H Me H H F H 933. CHF₂ H OCF₃ H H H H 934. CHF₂ H F F H H H 935. CHF₂ H OMe H H Cl H 936. Cl Cl H H H H H 937. Cl Cl F H H H H 938. Cl Cl F H H F H 939. Cl Cl F H H H F 940. Cl Cl F Me H H F 941. Cl Cl F H H H Cl 942. Cl Cl CF₃ H H H H 943. Cl Cl Me H H H H 944. Cl Cl F H H H CF₃ 945. Cl Cl F CF₃ H H F 946. Cl Cl Br H H H H 947. Cl Cl I H H H H 948. Cl Cl Cl H H H H 949. Cl Cl Cl H Cl H H 950. Cl Cl Cl H H H Cl 951. Cl Cl H Cl Cl H H 952. Cl Cl Cl Cl Cl H H 953. Cl Cl Cl Cl H Cl H 954. Cl Cl Cl Cl Cl H Cl 955. Cl Cl Cl Cl Cl Cl H 956. Cl Cl Cl Cl Cl Cl Cl 957. Cl Cl Cl Cl H H Cl 958. Cl Cl Cl H Cl Cl H 959. Cl Cl Cl H H Cl Cl 960. Cl Cl H Cl Cl Cl H 961. Cl Cl NO₂ H H H H 962. Cl Cl H Cl H H H 963. Cl Cl H H Cl H H 964. Cl Cl Cl H Cl H Cl 965. Cl Cl Cl Cl H H H 966. Cl Cl Cl H H Cl H 967. Cl Cl H Cl H Cl H 968. Cl Cl H OMe H H H 969. Cl Cl C(O)OMe H H H H 970. Cl Cl F Cl H H H 971. Cl Cl F Me H H H 972. Cl Cl H Me H H H 973. Cl Cl OMe H H H H 974. Cl Cl F F F H H 975. Cl Cl F F H F H 976. Cl Cl H F F F H 977. Cl Cl F H F F H 978. Cl Cl Me H Me H H 979. Cl Cl Me H H Me H 980. Cl Cl F H H CF₃ H 981. Cl Cl F H Br H H 982. Cl Cl Me Me H H H 983. Cl Cl F F F F F 984. Cl Cl F H H H OMe 985. Cl Cl Cl H F H H 986. Cl Cl NO₂ H Cl H H 987. Cl Cl NO₂ H H Me H 988. Cl Cl F H H H I 989. Cl Cl F H H H Br 990. Cl Cl Br H H H Br 991. Cl Cl Cl H H H Me 992. Cl Cl Cl H H H OCHF₂ 993. Cl Cl Cl H H H OMe 994. Cl Cl Me H H H OMe 995. Cl Cl OEt H H H CF₃ 996. Cl Cl OC(O)Me H H H H 997. Cl Cl OEt H H H Me 998. Cl Cl Me Me H H Me 999. Cl Cl Cl H H H C(O)OMe 1000. Cl Cl Cl H H OMe H 1001. Cl Cl F F H F F 1002. Cl Cl Cl H H F H 1003. Cl Cl F H H F Cl 1004. Cl Cl F H H Cl H 1005. Cl Cl Cl H H CF₃ H 1006. Cl Cl Cl Me H H H 1007. Cl Cl OCHF₂ H H H H 1008. Cl Cl OCH₂CF₃ H H H H 1009. Cl Cl CF₃ H H H OCHF₂ 1010. Cl Cl CF₃ H H H OCH₂CF₃ 1011. Cl Cl Me H H H Me 1012. Cl Cl Cl H H H F 1013. Cl Cl F H F H H 1014. Cl Cl F Me H H Cl 1015. Cl Cl F H H OMe H 1016. Cl Cl Cl H OCH₂O H 1017. Cl Cl Me H H F H 1018. Cl Cl OCF₃ H H H H 1019. Cl Cl F F H H H 1020. Cl Cl OMe H H Cl H 1021. Me Cl H H H H H 1022. Me Cl F H H H H 1023. Me Cl F H H F H 1024. Me Cl F H H H F 1025. Me Cl F Me H H F 1026. Me Cl F H H H Cl 1027. Me Cl CF₃ H H H H 1028. Me Cl Me H H H H 1029. Me Cl F H H H CF₃ 1030. Me Cl F CF₃ H H F 1031. Me Cl Br H H H H 1032. Me Cl I H H H H 1033. Me Cl Cl H H H H 1034. Me Cl Cl H Cl H H 1035. Me Cl Cl H H H Cl 1036. Me Cl H Cl Cl H H 1037. Me Cl Cl Cl Cl H H 1038. Me Cl Cl Cl H Cl H 1039. Me Cl Cl Cl Cl H Cl 1040. Me Cl Cl Cl Cl Cl H 1041. Me Cl Cl Cl Cl Cl Cl 1042. Me Cl Cl Cl H H Cl 1043. Me Cl Cl H Cl Cl H 1044. Me Cl Cl H H Cl Cl 1045. Me Cl H Cl Cl Cl H 1046. Me Cl NO₂ H H H H 1047. Me Cl H Cl H H H 1048. Me Cl H H Cl H H 1049. Me Cl Cl H Cl H Cl 1050. Me Cl Cl Cl H H H 1051. Me Cl Cl H H Cl H 1052. Me Cl H Cl H Cl H 1053. Me Cl H OMe H H H 1054. Me Cl C(O)OMe H H H H 1055. Me Cl F Cl H H H 1056. Me Cl F Me H H H 1057. Me Cl H Me H H H 1058. Me Cl OMe H H H H 1059. Me Cl F F F H H 1060. Me Cl F F H F H 1061. Me Cl H F F F H 1062. Me Cl F H F F H 1063. Me Cl Me H Me H H 1064. Me Cl Me H H Me H 1065. Me Cl F H H CF₃ H 1066. Me Cl F H Br H H 1067. Me Cl Me Me H H H 1068. Me Cl F F F F F 1069. Me Cl F H H H OMe 1070. Me Cl Cl H F H H 1071. Me Cl NO₂ H Cl H H 1072. Me Cl NO₂ H H Me H 1073. Me Cl F H H H I 1074. Me Cl F H H H Br 1075. Me Cl Br H H H Br 1076. Me Cl Cl H H H Me 1077. Me Cl Cl H H H OCHF₂ 1078. Me Cl Cl H H H OMe 1079. Me Cl Me H H H OMe 1080. Me Cl OEt H H H CF₃ 1081. Me Cl OC(O)Me H H H H 1082. Me Cl OEt H H H Me 1083. Me Cl Me Me H H Me 1084. Me Cl Cl H H H C(O)OMe 1085. Me Cl Cl H H OMe H 1086. Me Cl F F H F F 1087. Me Cl Cl H H F H 1088. Me Cl F H H F Cl 1089. Me Cl F H H Cl H 1090. Me Cl Cl H H CF₃ H 1091. Me Cl Cl Me H H H 1092. Me Cl OCHF₂ H H H H 1093. Me Cl OCH₂CF₃ H H H H 1094. Me Cl CF₃ H H H OCHF₂ 1095. Me Cl CF₃ H H H OCH₂CF₃ 1096. Me Cl Me H H H Me 1097. Me Cl Cl H H H F 1098. Me Cl F H F H H 1099. Me Cl F Me H H Cl 1100. Me Cl F H H OMe H 1101. Me Cl Cl H OCH₂O H 1102. Me Cl Me H H F H 1103. Me Cl OCF₃ H H H H 1104. Me Cl F F H H H 1105. Me Cl OMe H H Cl H 1106. Cl Me H H H H H 1107. Cl Me F H H H H 1108. Cl Me F H H F H 1109. Cl Me F H H H F 1110. Cl Me F Me H H F 1111. Cl Me F H H H Cl 1112. Cl Me CF₃ H H H H 1113. Cl Me Me H H H H 1114. Cl Me F H H H CF₃ 1115. Cl Me F CF₃ H H F 1116. Cl Me Br H H H H 1117. Cl Me I H H H H 1118. Cl Me Cl H H H H 1119. Cl Me Cl H Cl H H 1120. Cl Me Cl H H H Cl 1121. Cl Me H Cl Cl H H 1122. Cl Me Cl Cl Cl H H 1123. Cl Me Cl Cl H Cl H 1124. Cl Me Cl Cl Cl H Cl 1125. Cl Me Cl Cl Cl Cl H 1126. Cl Me Cl Cl Cl Cl Cl 1127. Cl Me Cl Cl H H Cl 1128. Cl Me Cl H Cl Cl H 1129. Cl Me Cl H H Cl Cl 1130. Cl Me H Cl Cl Cl H 1131. Cl Me NO₂ H H H H 1132. Cl Me H Cl H H H 1133. Cl Me H H Cl H H 1134. Cl Me Cl H Cl H Cl 1135. Cl Me Cl Cl H H H 1136. Cl Me Cl H H Cl H 1137. Cl Me H Cl H Cl H 1138. Cl Me H OMe H H H 1139. Cl Me C(O)OMe H H H H 1140. Cl Me F Cl H H H 1141. Cl Me F Me H H H 1142. Cl Me H Me H H H 1143. Cl Me OMe H H H H 1144. Cl Me F F F H H 1145. Cl Me F F H F H 1146. Cl Me H F F F H 1147. Cl Me F H F F H 1148. Cl Me Me H Me H H 1149. Cl Me Me H H Me H 1150. Cl Me F H H CF₃ H 1151. Cl Me F H Br H H 1152. Cl Me Me Me H H H 1153. Cl Me F F F F F 1154. Cl Me F H H H OMe 1155. Cl Me Cl H F H H 1156. Cl Me NO₂ H Cl H H 1157. Cl Me NO₂ H H Me H 1158. Cl Me F H H H I 1159. Cl Me F H H H Br 1160. Cl Me Br H H H Br 1161. Cl Me Cl H H H Me 1162. Cl Me Cl H H H OCHF₂ 1163. Cl Me Cl H H H OMe 1164. Cl Me Me H H H OMe 1165. Cl Me OEt H H H CF₃ 1166. Cl Me OC(O)Me H H H H 1167. Cl Me OEt H H H Me 1168. Cl Me Me Me H H Me 1169. Cl Me Cl H H H C(O)OMe 1170. Cl Me Cl H H OMe H 1171. Cl Me F F H F F 1172. Cl Me Cl H H F H 1173. Cl Me F H H F Cl 1174. Cl Me F H H Cl H 1175. Cl Me Cl H H CF₃ H 1176. Cl Me Cl Me H H H 1177. Cl Me OCHF₂ H H H H 1178. Cl Me OCH₂CF₃ H H H H 1179. Cl Me CF₃ H H H OCHF₂ 1180. Cl Me CF₃ H H H OCH₂CF₃ 1181. Cl Me Me H H H Me 1182. Cl Me Cl H H H F 1183. Cl Me F H F H H 1184. Cl Me F Me H H Cl 1185. Cl Me F H H OMe H 1186. Cl Me Cl H OCH₂O H 1187. Cl Me Me H H F H 1188. Cl Me OCF₃ H H H H 1189. Cl Me F F H H H 1190. Cl Me OMe H H Cl H

TABLE 2 Compounds of the formula Ia-R ( Ia-R )

Ex. No. R¹¹ R¹² R¹ R² R³ R⁴ R⁵ 1191. H H H H H H H 1192. H H F H H H H 1193. H H F H H F H 1194. H H F H H H F 1195. H H F Me H H F 1196. H H F H H H Cl 1197. H H CF₃ H H H H 1198. H H Me H H H H 1199. H H F H H H CF₃ 1200. H H F CF₃ H H F 1201. H H Br H H H H 1202. H H I H H H H 1203. H H Cl H H H H 1204. H H Cl H Cl H H 1205. H H Cl H H H Cl 1206. H H H Cl Cl H H 1207. H H Cl Cl Cl H H 1208. H H Cl Cl H Cl H 1209. H H Cl Cl Cl H Cl 1210. H H Cl Cl Cl Cl H 1211. H H Cl Cl Cl Cl Cl 1212. H H Cl Cl H H Cl 1213. H H Cl H Cl Cl H 1214. H H Cl H H Cl Cl 1215. H H H Cl Cl Cl H 1216. H H NO₂ H H H H 1217. H H H Cl H H H 1218. H H H H Cl H H 1219. H H Cl H Cl H Cl 1220. H H Cl Cl H H H 1221. H H Cl H H Cl H 1222. H H H Cl H Cl H 1223. H H H OMe H H H 1224. H H C(O)OMe H H H H 1225. H H F Cl H H H 1226. H H F Me H H H 1227. H H H Me H H H 1228. H H OMe H H H H 1229. H H F F F H H 1230. H H F F H F H 1231. H H H F F F H 1232. H H F H F F H 1233. H H Me H Me H H 1234. H H Me H H Me H 1235. H H F H H CF₃ H 1236. H H F H Br H H 1237. H H Me Me H H H 1238. H H F F F F F 1239. H H F H H H OMe 1240. H H Cl H F H H 1241. H H NO₂ H Cl H H 1242. H H NO₂ H H Me H 1243. H H F H H H I 1244. H H F H H H Br 1245. H H Br H H H Br 1246. H H Cl H H H Me 1247. H H Cl H H H OCHF₂ 1248. H H Cl H H H OMe 1249. H H Me H H H OMe 1250. H H OEt H H H CF₃ 1251. H H OC(O)Me H H H H 1252. H H OEt H H H Me 1253. H H Me Me H H Me 1254. H H Cl H H H C(O)OMe 1255. H H Cl H H OMe H 1256. H H F F H F F 1257. H H Cl H H F H 1258. H H F H H F Cl 1259. H H F H H Cl H 1260. H H Cl H H CF₃ H 1261. H H Cl Me H H H 1262. H H OCHF₂ H H H H 1263. H H OCH₂CF₃ H H H H 1264. H H CF₃ H H H OCHF₂ 1265. H H CF₃ H H H OCH₂CF₃ 1266. H H Me H H H Me 1267. H H Cl H H H F 1268. H H F H F H H 1269. H H F Me H H Cl 1270. H H F H H OMe H 1271. H H Cl H OCH₂O H 1272. H H Me H H F H 1273. H H OCF₃ H H H H 1274. H H F F H H H 1275. H H OMe H H Cl H 1276. F H H H H H H 1277. F H F H H H H 1278. F H F H H F H 1279. F H F H H H F 1280. F H F Me H H F 1281. F H F H H H Cl 1282. F H CF₃ H H H H 1283. F H Me H H H H 1284. F H F H H H CF₃ 1285. F H F CF₃ H H F 1286. F H Br H H H H 1287. F H I H H H H 1288. F H Cl H H H H 1289. F H Cl H Cl H H 1290. F H Cl H H H Cl 1291. F H H Cl Cl H H 1292. F H Cl Cl Cl H H 1293. F H Cl Cl H Cl H 1294. F H Cl Cl Cl H Cl 1295. F H Cl Cl Cl Cl H 1296. F H Cl Cl Cl Cl Cl 1297. F H Cl Cl H H Cl 1298. F H Cl H Cl Cl H 1299. F H Cl H H Cl Cl 1300. F H H Cl Cl Cl H 1301. F H NO₂ H H H H 1302. F H H Cl H H H 1303. F H H H Cl H H 1304. F H Cl H Cl H Cl 1305. F H Cl Cl H H H 1306. F H Cl H H Cl H 1307. F H H Cl H Cl H 1308. F H H OMe H H H 1309. F H C(O)OMe H H H H 1310. F H F Cl H H H 1311. F H F Me H H H 1312. F H H Me H H H 1313. F H OMe H H H H 1314. F H F F F H H 1315. F H F F H F H 1316. F H H F F F H 1317. F H F H F F H 1318. F H Me H Me H H 1319. F H Me H H Me H 1320. F H F H H CF₃ H 1321. F H F H Br H H 1322. F H Me Me H H H 1323. F H F F F F F 1324. F H F H H H OMe 1325. F H Cl H F H H 1326. F H NO₂ H Cl H H 1327. F H NO₂ H H Me H 1328. F H F H H H I 1329. F H F H H H Br 1330. F H Br H H H Br 1331. F H Cl H H H Me 1332. F H Cl H H H OCHF₂ 1333. F H Cl H H H OMe 1334. F H Me H H H OMe 1335. F H OEt H H H CF₃ 1336. F H OC(O)Me H H H H 1337. F H OEt H H H Me 1338. F H Me Me H H Me 1339. F H Cl H H H C(O)OMe 1340. F H Cl H H OMe H 1341. F H F F H F F 1342. F H Cl H H F H 1343. F H F H H F Cl 1344. F H F H H Cl H 1345. F H Cl H H CF₃ H 1346. F H Cl Me H H H 1347. F H OCHF₂ H H H H 1348. F H OCH₂CF₃ H H H H 1349. F H CF₃ H H H OCHF₂ 1350. F H CF₃ H H H OCH₂CF₃ 1351. F H Me H H H Me 1352. F H Cl H H H F 1353. F H F H F H H 1354. F H F Me H H Cl 1355. F H F H H OMe H 1356. F H Cl H OCH₂O H 1357. F H Me H H F H 1358. F H OCF₃ H H H H 1359. F H F F H H H 1360. F H OMe H H Cl H 1361. Cl H H H H H H 1362. Cl H F H H H H 1363. Cl H F H H F H 1364. Cl H F H H H F 1365. Cl H F Me H H F 1366. Cl H F H H H Cl 1367. Cl H CF₃ H H H H 1368. Cl H Me H H H H 1369. Cl H F H H H CF₃ 1370. Cl H F CF₃ H H F 1371. Cl H Br H H H H 1372. Cl H I H H H H 1373. Cl H Cl H H H H 1374. Cl H Cl H Cl H H 1375. Cl H Cl H H H Cl 1376. Cl H H Cl Cl H H 1377. Cl H Cl Cl Cl H H 1378. Cl H Cl Cl H Cl H 1379. Cl H Cl Cl Cl H Cl 1380. Cl H Cl Cl Cl Cl H 1381. Cl H Cl Cl Cl Cl Cl 1382. Cl H Cl Cl H H Cl 1383. Cl H Cl H Cl Cl H 1384. Cl H Cl H H Cl Cl 1385. Cl H H Cl Cl Cl H 1386. Cl H NO₂ H H H H 1387. Cl H H Cl H H H 1388. Cl H H H Cl H H 1389. Cl H Cl H Cl H Cl 1390. Cl H Cl Cl H H H 1391. Cl H Cl H H Cl H 1392. Cl H H Cl H Cl H 1393. Cl H H OMe H H H 1394. Cl H C(O)OMe H H H H 1395. Cl H F Cl H H H 1396. Cl H F Me H H H 1397. Cl H H Me H H H 1398. Cl H OMe H H H H 1399. Cl H F F F H H 1400. Cl H F F H F H 1401. Cl H H F F F H 1402. Cl H F H F F H 1403. Cl H Me H Me H H 1404. Cl H Me H H Me H 1405. Cl H F H H CF₃ H 1406. Cl H F H Br H H 1407. Cl H Me Me H H H 1408. Cl H F F F F F 1409. Cl H F H H H OMe 1410. Cl H Cl H F H H 1411. Cl H NO₂ H Cl H H 1412. Cl H NO₂ H H Me H 1413. Cl H F H H H I 1414. Cl H F H H H Br 1415. Cl H Br H H H Br 1416. Cl H Cl H H H Me 1417. Cl H Cl H H H OCHF₂ 1418. Cl H Cl H H H OMe 1419. Cl H Me H H H OMe 1420. Cl H OEt H H H CF₃ 1421. Cl H OC(O)Me H H H H 1422. Cl H OEt H H H Me 1423. Cl H Me Me H H Me 1424. Cl H Cl H H H C(O)OMe 1425. Cl H Cl H H OMe H 1426. Cl H F F H F F 1427. Cl H Cl H H F H 1428. Cl H F H H F Cl 1429. Cl H F H H Cl H 1430. Cl H Cl H H CF₃ H 1431. Cl H Cl Me H H H 1432. Cl H OCHF₂ H H H H 1433. Cl H OCH₂CF₃ H H H H 1434. Cl H CF₃ H H H OCHF₂ 1435. Cl H CF₃ H H H OCH₂CF₃ 1436. Cl H Me H H H Me 1437. Cl H Cl H H H F 1438. Cl H F H F H H 1439. Cl H F Me H H Cl 1440. Cl H F H H OMe H 1441. Cl H Cl H OCH₂O H 1442. Cl H Me H H F H 1443. Cl H OCF₃ H H H H 1444. Cl H F F H H H 1445. Cl H OMe H H Cl H 1446. Br H H H H H H 1447. Br H F H H H H 1448. Br H F H H F H 1449. Br H F H H H F 1450. Br H F Me H H F 1451. Br H F H H H Cl 1452. Br H CF₃ H H H H 1453. Br H Me H H H H 1454. Br H F H H H CF₃ 1455. Br H F CF₃ H H F 1456. Br H Br H H H H 1457. Br H I H H H H 1458. Br H Cl H H H H 1459. Br H Cl H Cl H H 1460. Br H Cl H H H Cl 1461. Br H H Cl Cl H H 1462. Br H Cl Cl Cl H H 1463. Br H Cl Cl H Cl H 1464. Br H Cl Cl Cl H Cl 1465. Br H Cl Cl Cl Cl H 1466. Br H Cl Cl Cl Cl Cl 1467. Br H Cl Cl H H Cl 1468. Br H Cl H Cl Cl H 1469. Br H Cl H H Cl Cl 1470. Br H H Cl Cl Cl H 1471. Br H NO₂ H H H H 1472. Br H H Cl H H H 1473. Br H H H Cl H H 1474. Br H Cl H Cl H Cl 1475. Br H Cl Cl H H H 1476. Br H Cl H H Cl H 1477. Br H H Cl H Cl H 1478. Br H H OMe H H H 1479. Br H C(O)OMe H H H H 1480. Br H F Cl H H H 1481. Br H F Me H H H 1482. Br H H Me H H H 1483. Br H OMe H H H H 1484. Br H F F F H H 1485. Br H F F H F H 1486. Br H H F F F H 1487. Br H F H F F H 1488. Br H Me H Me H H 1489. Br H Me H H Me H 1490. Br H F H H CF₃ H 1491. Br H F H Br H H 1492. Br H Me Me H H H 1493. Br H F F F F F 1494. Br H F H H H OMe 1495. Br H Cl H F H H 1496. Br H NO₂ H Cl H H 1497. Br H NO₂ H H Me H 1498. Br H F H H H I 1499. Br H F H H H Br 1500. Br H Br H H H Br 1501. Br H Cl H H H Me 1502. Br H Cl H H H OCHF₂ 1503. Br H Cl H H H OMe 1504. Br H Me H H H OMe 1505. Br H OEt H H H CF₃ 1506. Br H OC(O)Me H H H H 1507. Br H OEt H H H Me 1508. Br H Me Me H H Me 1509. Br H Cl H H H C(O)OMe 1510. Br H Cl H H OMe H 1511. Br H F F H F F 1512. Br H Cl H H F H 1513. Br H F H H F Cl 1514. Br H F H H Cl H 1515. Br H Cl H H CF₃ H 1516. Br H Cl Me H H H 1517. Br H OCHF₂ H H H H 1518. Br H OCH₂CF₃ H H H H 1519. Br H CF₃ H H H OCHF₂ 1520. Br H CF₃ H H H OCH₂CF₃ 1521. Br H Me H H H Me 1522. Br H Cl H H H F 1523. Br H F H F H H 1524. Br H F Me H H Cl 1525. Br H F H H OMe H 1526. Br H Cl H OCH₂O H 1527. Br H Me H H F H 1528. Br H OCF₃ H H H H 1529. Br H F F H H H 1530. Br H OMe H H Cl H 1531. I H H H H H H 1532. I H F H H H H 1533. I H F H H F H 1534. I H F H H H F 1535. I H F Me H H F 1536. I H F H H H Cl 1537. I H CF₃ H H H H 1538. I H Me H H H H 1539. I H F H H H CF₃ 1540. I H F CF₃ H H F 1541. I H Br H H H H 1542. I H I H H H H 1543. I H Cl H H H H 1544. I H Cl H Cl H H 1545. I H Cl H H H Cl 1546. I H H Cl Cl H H 1547. I H Cl Cl Cl H H 1548. I H Cl Cl H Cl H 1549. I H Cl Cl Cl H Cl 1550. I H Cl Cl Cl Cl H 1551. I H Cl Cl Cl Cl Cl 1552. I H Cl Cl H H Cl 1553. I H Cl H Cl Cl H 1554. I H Cl H H Cl Cl 1555. I H H Cl Cl Cl H 1556. I H NO₂ H H H H 1557. I H H Cl H H H 1558. I H H H Cl H H 1559. I H Cl H Cl H Cl 1560. I H Cl Cl H H H 1561. I H Cl H H Cl H 1562. I H H Cl H Cl H 1563. I H H OMe H H H 1564. I H C(O)OMe H H H H 1565. I H F Cl H H H 1566. I H F Me H H H 1567. I H H Me H H H 1568. I H OMe H H H H 1569. I H F F F H H 1570. I H F F H F H 1571. I H H F F F H 1572. I H F H F F H 1573. I H Me H Me H H 1574. I H Me H H Me H 1575. I H F H H CF₃ H 1576. I H F H Br H H 1577. I H Me Me H H H 1578. I H F F F F F 1579. I H F H H H OMe 1580. I H Cl H F H H 1581. I H NO₂ H Cl H H 1582. I H NO₂ H H Me H 1583. I H F H H H I 1584. I H F H H H Br 1585. I H Br H H H Br 1586. I H Cl H H H Me 1587. I H Cl H H H OCHF₂ 1588. I H Cl H H H OMe 1589. I H Me H H H OMe 1590. I H OEt H H H CF₃ 1591. I H OC(O)Me H H H H 1592. I H OEt H H H Me 1593. I H Me Me H H Me 1594. I H Cl H H H C(O)OMe 1595. I H Cl H H OMe H 1596. I H F F H F F 1597. I H Cl H H F H 1598. I H F H H F Cl 1599. I H F H H Cl H 1600. I H Cl H H CF₃ H 1601. I H Cl Me H H H 1602. I H OCHF₂ H H H H 1603. I H OCH₂CF₃ H H H H 1604. I H CF₃ H H H OCHF₂ 1605. I H CF₃ H H H OCH₂CF₃ 1606. I H Me H H H Me 1607. I H Cl H H H F 1608. I H F H F H H 1609. I H F Me H H Cl 1610. I H F H H OMe H 1611. I H Cl H OCH₂O H 1612. I H Me H H F H 1613. I H OCF₃ H H H H 1614. I H F F H H H 1615. I H OMe H H Cl H 1616. H Cl H H H H H 1617. H Cl F H H H H 1618. H Cl F H H F H 1619. H Cl F H H H F 1620. H Cl F Me H H F 1621. H Cl F H H H Cl 1622. H Cl CF₃ H H H H 1623. H Cl Me H H H H 1624. H Cl F H H H CF₃ 1625. H Cl F CF₃ H H F 1626. H Cl Br H H H H 1627. H Cl I H H H H 1628. H Cl Cl H H H H 1629. H Cl Cl H Cl H H 1630. H Cl Cl H H H Cl 1631. H Cl H Cl Cl H H 1632. H Cl Cl Cl Cl H H 1633. H Cl Cl Cl H Cl H 1634. H Cl Cl Cl Cl H Cl 1635. H Cl Cl Cl Cl Cl H 1636. H Cl Cl Cl Cl Cl Cl 1637. H Cl Cl Cl H H Cl 1638. H Cl Cl H Cl Cl H 1639. H Cl Cl H H Cl Cl 1640. H Cl H Cl Cl Cl H 1641. H Cl NO₂ H H H H 1642. H Cl H Cl H H H 1643. H Cl H H Cl H H 1644. H Cl Cl H Cl H Cl 1645. H Cl Cl Cl H H H 1646. H Cl Cl H H Cl H 1647. H Cl H Cl H Cl H 1648. H Cl H OMe H H H 1649. H Cl C(O)OMe H H H H 1650. H Cl F Cl H H H 1651. H Cl F Me H H H 1652. H Cl H Me H H H 1653. H Cl OMe H H H H 1654. H Cl F F F H H 1655. H Cl F F H F H 1656. H Cl H F F F H 1657. H Cl F H F F H 1658. H Cl Me H Me H H 1659. H Cl Me H H Me H 1660. H Cl F H H CF₃ H 1661. H Cl F H Br H H 1662. H Cl Me Me H H H 1663. H Cl F F F F F 1664. H Cl F H H H OMe 1665. H Cl Cl H F H H 1666. H Cl NO₂ H Cl H H 1667. H Cl NO₂ H H Me H 1668. H Cl F H H H I 1669. H Cl F H H H Br 1670. H Cl Br H H H Br 1671. H Cl Cl H H H Me 1672. H Cl Cl H H H OCHF₂ 1673. H Cl Cl H H H OMe 1674. H Cl Me H H H OMe 1675. H Cl OEt H H H CF₃ 1676. H Cl OC(O)Me H H H H 1677. H Cl OEt H H H Me 1678. H Cl Me Me H H Me 1679. H Cl Cl H H H C(O)OMe 1680. H Cl Cl H H OMe H 1681. H Cl F F H F F 1682. H Cl Cl H H F H 1683. H Cl F H H F Cl 1684. H Cl F H H Cl H 1685. H Cl Cl H H CF₃ H 1686. H Cl Cl Me H H H 1687. H Cl OCHF₂ H H H H 1688. H Cl OCH₂CF₃ H H H H 1689. H Cl CF₃ H H H OCHF₂ 1690. H Cl CF₃ H H H OCH₂CF₃ 1691. H Cl Me H H H Me 1692. H Cl Cl H H H F 1693. H Cl F H F H H 1694. H Cl F Me H H Cl 1695. H Cl F H H OMe H 1696. H Cl Cl H OCH₂O H 1697. H Cl Me H H F H 1698. H Cl OCF₃ H H H H 1699. H Cl F F H H H 1700. H Cl OMe H H Cl H 1701. H Br H H H H H 1702. H Br F H H H H 1703. H Br F H H F H 1704. H Br F H H H F 1705. H Br F Me H H F 1706. H Br F H H H Cl 1707. H Br CF₃ H H H H 1708. H Br Me H H H H 1709. H Br F H H H CF₃ 1710. H Br F CF₃ H H F 1711. H Br Br H H H H 1712. H Br I H H H H 1713. H Br Cl H H H H 1714. H Br Cl H Cl H H 1715. H Br Cl H H H Cl 1716. H Br H Cl Cl H H 1717. H Br Cl Cl Cl H H 1718. H Br Cl Cl H Cl H 1719. H Br Cl Cl Cl H Cl 1720. H Br Cl Cl Cl Cl H 1721. H Br Cl Cl Cl Cl Cl 1722. H Br Cl Cl H H Cl 1723. H Br Cl H Cl Cl H 1724. H Br Cl H H Cl Cl 1725. H Br H Cl Cl Cl H 1726. H Br NO₂ H H H H 1727. H Br H Cl H H H 1728. H Br H H Cl H H 1729. H Br Cl H Cl H Cl 1730. H Br Cl Cl H H H 1731. H Br Cl H H Cl H 1732. H Br H Cl H Cl H 1733. H Br H OMe H H H 1734. H Br C(O)OMe H H H H 1735. H Br F Cl H H H 1736. H Br F Me H H H 1737. H Br H Me H H H 1738. H Br OMe H H H H 1739. H Br F F F H H 1740. H Br F F H F H 1741. H Br H F F F H 1742. H Br F H F F H 1743. H Br Me H Me H H 1744. H Br Me H H Me H 1745. H Br F H H CF₃ H 1746. H Br F H Br H H 1747. H Br Me Me H H H 1748. H Br F F F F F 1749. H Br F H H H OMe 1750. H Br Cl H F H H 1751. H Br NO₂ H Cl H H 1752. H Br NO₂ H H Me H 1753. H Br F H H I I 1754. H Br F H H H Br 1755. H Br Br H H H Br 1756. H Br Cl H H H Me 1757. H Br Cl H H H OCHF₂ 1758. H Br Cl H H H OMe 1759. H Br Me H H H OMe 1760. H Br OEt H H H CF₃ 1761. H Br OC(O)Me H H H H 1762. H Br OEt H H H Me 1763. H Br Me Me H H Me 1764. H Br Cl H H H C(O)OMe 1765. H Br Cl H H OMe H 1766. H Br F F H F F 1767. H Br Cl H H F H 1768. H Br F H H F Cl 1769. H Br F H H Cl H 1770. H Br Cl H H CF₃ H 1771. H Br Cl Me H H H 1772. H Br OCHF₂ H H H H 1773. H Br OCH₂CF₃ H H H H 1774. H Br CF₃ H H H OCHF₂ 1775. H Br CF₃ H H H OCH₂CF₃ 1776. H Br Me H H H Me 1777. H Br Cl H H H F 1778. H Br F H F H H 1779. H Br F Me H H Cl 1780. H Br F H H OMe H 1781. H Br Cl H OCH₂O H 1782. H Br Me H H F H 1783. H Br OCF₃ H H H H 1784. H Br F F H H H 1785. H Br OMe H H Cl H 1786. Me H H H H H H 1787. Me H F H H H H 1788. Me H F H H F H 1789. Me H F H H H F 1790. Me H F Me H H F 1791. Me H F H H H Cl 1792. Me H CF₃ H H H H 1793. Me H Me H H H H 1794. Me H F H H H CF₃ 1795. Me H F CF₃ H H F 1796. Me H Br H H H H 1797. Me H I H H H H 1798. Me H Cl H H H H 1799. Me H Cl H Cl H H 1800. Me H Cl H H H Cl 1801. Me H H Cl Cl H H 1802. Me H Cl Cl Cl H H 1803. Me H Cl Cl H Cl H 1804. Me H Cl Cl Cl H Cl 1805. Me H Cl Cl Cl Cl H 1806. Me H Cl Cl Cl Cl Cl 1807. Me H Cl Cl H H Cl 1808. Me H Cl H Cl Cl H 1809. Me H Cl H H Cl Cl 1810. Me H H Cl Cl Cl H 1811. Me H NO₂ H H H H 1812. Me H H Cl H H H 1813. Me H H H Cl H H 1814. Me H Cl H Cl H Cl 1815. Me H Cl Cl H H H 1816. Me H Cl H H Cl H 1817. Me H H Cl H Cl H 1818. Me H H OMe H H H 1819. Me H C(O)OMe H H H H 1820. Me H F Cl H H H 1821. Me H F Me H H H 1822. Me H H Me H H H 1823. Me H OMe H H H H 1824. Me H F F F H H 1825. Me H F F H F H 1826. Me H H F F F H 1827. Me H F H F F H 1828. Me H Me H Me H H 1829. Me H Me H H Me H 1830. Me H F H H CF₃ H 1831. Me H F H Br H H 1832. Me H Me Me H H H 1833. Me H F F F F F 1834. Me H F H H H OMe 1835. Me H Cl H F H H 1836. Me H NO₂ H Cl H H 1837. Me H NO₂ H H Me H 1838. Me H F H H H I 1839. Me H F H H H Br 1840. Me H Br H H H Br 1841. Me H Cl H H H Me 1842. Me H Cl H H H OCHF₂ 1843. Me H Cl H H H OMe 1844. Me H Me H H H OMe 1845. Me H OEt H H H CF₃ 1846. Me H OC(O)Me H H H H 1847. Me H OEt H H H Me 1848. Me H Me Me H H Me 1849. Me H Cl H H H C(O)OMe 1850. Me H Cl H H OMe H 1851. Me H F F H F F 1852. Me H Cl H H F H 1853. Me H F H H F Cl 1854. Me H F H H Cl H 1855. Me H Cl H H CF₃ H 1856. Me H Cl Me H H H 1857. Me H OCHF₂ H H H H 1858. Me H OCH₂CF₃ H H H H 1859. Me H CF₃ H H H OCHF₂ 1860. Me H CF₃ H H H OCH₂CF₃ 1861. Me H Me H H H Me 1862. Me H Cl H H H F 1863. Me H F H F H H 1864. Me H F Me H H Cl 1865. Me H F H H OMe H 1866. Me H Cl H OCH₂O H 1867. Me H Me H H F H 1868. Me H OCF₃ H H H H 1869. Me H F F H H H 1870. Me H OMe H H Cl H 1871. H Me H H H H H 1872. H Me F H H H H 1873. H Me F H H F H 1874. H Me F H H H F 1875. H Me F Me H H F 1876. H Me F H H H Cl 1877. H Me CF₃ H H H H 1878. H Me Me H H H H 1879. H Me F H H H CF₃ 1880. H Me F CF₃ H H F 1881. H Me Br H H H H 1882. H Me I H H H H 1883. H Me Cl H H H H 1884. H Me Cl H Cl H H 1885. H Me Cl H H H Cl 1886. H Me H Cl Cl H H 1887. H Me Cl Cl Cl H H 1888. H Me Cl Cl H Cl H 1889. H Me Cl Cl Cl H Cl 1890. H Me Cl Cl Cl Cl H 1891. H Me Cl Cl Cl Cl Cl 1892. H Me Cl Cl H H Cl 1893. H Me Cl H Cl Cl H 1894. H Me Cl H H Cl Cl 1895. H Me H Cl Cl Cl H 1896. H Me NO₂ H H H H 1897. H Me H Cl H H H 1898. H Me H H Cl H H 1899. H Me Cl H Cl H Cl 1900. H Me Cl Cl H H H 1901. H Me Cl H H Cl H 1902. H Me H Cl H Cl H 1903. H Me H OMe H H H 1904. H Me C(O)OMe H H H H 1905. H Me F Cl H H H 1906. H Me F Me H H H 1907. H Me H Me H H H 1908. H Me OMe H H H H 1909. H Me F F F H H 1910. H Me F F H F H 1911. H Me H F F F H 1912. H Me F H F F H 1913. H Me Me H Me H H 1914. H Me Me H H Me H 1915. H Me F H H CF₃ H 1916. H Me F H Br H H 1917. H Me Me Me H H H 1918. H Me F F F F F 1919. H Me F H H H OMe 1920. H Me Cl H F H H 1921. H Me NO₂ H Cl H H 1922. H Me NO₂ H H Me H 1923. H Me F H H H I 1924. H Me F H H H Br 1925. H Me Br H H H Br 1926. H Me Cl H H H Me 1927. H Me Cl H H H OCHF₂ 1928. H Me Cl H H H OMe 1929. H Me Me H H H OMe 1930. H Me OEt H H H CF₃ 1931. H Me OC(O)Me H H H H 1932. H Me OEt H H H Me 1933. H Me Me Me H H Me 1934. H Me Cl H H H C(O)OMe 1935. H Me Cl H H OMe H 1936. H Me F F H F F 1937. H Me Cl H H F H 1938. H Me F H H F Cl 1939. H Me F H H Cl H 1940. H Me Cl H H CF₃ H 1941. H Me Cl Me H H H 1942. H Me OCHF₂ H H H H 1943. H Me OCH₂CF₃ H H H H 1944. H Me CF₃ H H H OCHF₂ 1945. H Me CF₃ H H H OCH₂CF₃ 1946. H Me Me H H H Me 1947. H Me Cl H H H F 1948. H Me F H F H H 1949. H Me F Me H H Cl 1950. H Me F H H OMe H 1951. H Me Cl H OCH₂O H 1952. H Me Me H H F H 1953. H Me OCF₃ H H H H 1954. H Me F F H H H 1955. H Me OMe H H Cl H 1956. NO₂ H H H H H H 1957. NO₂ H F H H H H 1958. NO₂ H F H H F H 1959. NO₂ H F H H H F 1960. NO₂ H F Me H H F 1961. NO₂ H F H H H Cl 1962. NO₂ H CF₃ H H H H 1963. NO₂ H Me H H H H 1964. NO₂ H F H H H CF₃ 1965. NO₂ H F CF₃ H H F 1966. NO₂ H Br H H H H 1967. NO₂ H I H H H H 1968. NO₂ H Cl H H H H 1969. NO₂ H Cl H Cl H H 1970. NO₂ H Cl H H H Cl 1971. NO₂ H H Cl Cl H H 1972. NO₂ H Cl Cl Cl H H 1973. NO₂ H Cl Cl H Cl H 1974. NO₂ H Cl Cl Cl H Cl 1975. NO₂ H Cl Cl Cl Cl H 1976. NO₂ H Cl Cl Cl Cl Cl 1977. NO₂ H Cl Cl H H Cl 1978. NO₂ H Cl H Cl Cl H 1979. NO₂ H Cl H H Cl Cl 1980. NO₂ H H Cl Cl Cl H 1981. NO₂ H NO₂ H H H H 1982. NO₂ H H Cl H H H 1983. NO₂ H H H Cl H H 1984. NO₂ H Cl H Cl H Cl 1985. NO₂ H Cl Cl H H H 1986. NO₂ H Cl H H Cl H 1987. NO₂ H H Cl H Cl H 1988. NO₂ H H OMe H H H 1989. NO₂ H C(O)OMe H H H H 1990. NO₂ H F Cl H H H 1991. NO₂ H F Me H H H 1992. NO₂ H H Me H H H 1993. NO₂ H OMe H H H H 1994. NO₂ H F F F H H 1995. NO₂ H F F H F H 1996. NO₂ H H F F F H 1997. NO₂ H F H F F H 1998. NO₂ H Me H Me H H 1999. NO₂ H Me H H Me H 2000. NO₂ H F H H CF₃ H 2001. NO₂ H F H Br H H 2002. NO₂ H Me Me H H H 2003. NO₂ H F F F F F 2004. NO₂ H F H H H OMe 2005. NO₂ H Cl H F H H 2006. NO₂ H NO₂ H Cl H H 2007. NO₂ H NO₂ H H Me H 2008. NO₂ H F H H H I 2009. NO₂ H F H H H Br 2010. NO₂ H Br H H H Br 2011. NO₂ H Cl H H H Me 2012. NO₂ H Cl H H H OCHF₂ 2013. NO₂ H Cl H H H OMe 2014. NO₂ H Me H H H OMe 2015. NO₂ H OEt H H H CF₃ 2016. NO₂ H OC(O)Me H H H H 2017. NO₂ H OEt H H H Me 2018. NO₂ H Me Me H H Me 2019. NO₂ H Cl H H H C(O)OMe 2020. NO₂ H Cl H H OMe H 2021. NO₂ H F F H F F 2022. NO₂ H Cl H H F H 2023. NO₂ H F H H F Cl 2024. NO₂ H F H H Cl H 2025. NO₂ H Cl H H CF₃ H 2026. NO₂ H Cl Me H H H 2027. NO₂ H OCHF₂ H H H H 2028. NO₂ H OCH₂CF₃ H H H H 2029. NO₂ H CF₃ H H H OCHF₂ 2030. NO₂ H CF₃ H H H OCH₂CF₃ 2031. NO₂ H Me H H H Me 2032. NO₂ H Cl H H H F 2033. NO₂ H F H F H H 2034. NO₂ H F Me H H Cl 2035. NO₂ H F H H OMe H 2036. NO₂ H Cl H OCH₂O H 2037. NO₂ H Me H H F H 2038. NO₂ H OCF₃ H H H H 2039. NO₂ H F F H H H 2040. NO₂ H OMe H H Cl H 2041. CHF₂ H H H H H H 2042. CHF₂ H F H H H H 2043. CHF₂ H F H H F H 2044. CHF₂ H F H H H F 2045. CHF₂ H F Me H H F 2046. CHF₂ H F H H H Cl 2047. CHF₂ H CF₃ H H H H 2048. CHF₂ H Me H H H H 2049. CHF₂ H F H H H CF₃ 2050. CHF₂ H F CF₃ H H F 2051. CHF₂ H Br H H H H 2052. CHF₂ H I H H H H 2053. CHF₂ H Cl H H H H 2054. CHF₂ H Cl H Cl H H 2055. CHF₂ H Cl H H H Cl 2056. CHF₂ H H Cl Cl H H 2057. CHF₂ H Cl Cl Cl H H 2058. CHF₂ H Cl Cl H Cl H 2059. CHF₂ H Cl Cl Cl H Cl 2060. CHF₂ H Cl Cl Cl Cl H 2061. CHF₂ H Cl Cl Cl Cl Cl 2062. CHF₂ H Cl Cl H H Cl 2063. CHF₂ H Cl H Cl Cl H 2064. CHF₂ H Cl H H Cl Cl 2065. CHF₂ H H Cl Cl Cl H 2066. CHF₂ H NO₂ H H H H 2067. CHF₂ H H Cl H H H 2068. CHF₂ H H H Cl H H 2069. CHF₂ H Cl H Cl H Cl 2070. CHF₂ H Cl Cl H H H 2071. CHF₂ H Cl H H Cl H 2072. CHF₂ H H Cl H Cl H 2073. CHF₂ H H OMe H H H 2074. CHF₂ H C(O)OMe H H H H 2075. CHF₂ H F Cl H H H 2076. CHF₂ H F Me H H H 2077. CHF₂ H H Me H H H 2078. CHF₂ H OMe H H H H 2079. CHF₂ H F F F H H 2080. CHF₂ H F F H F H 2081. CHF₂ H H F F F H 2082. CHF₂ H F H F F H 2083. CHF₂ H Me H Me H H 2084. CHF₂ H Me H H Me H 2085. CHF₂ H F H H CF₃ H 2086. CHF₂ H F H Br H H 2087. CHF₂ H Me Me H H H 2088. CHF₂ H F F F F F 2089. CHF₂ H F H H H OMe 2090. CHF₂ H Cl H F H H 2091. CHF₂ H NO₂ H Cl H H 2092. CHF₂ H NO₂ H H Me H 2093. CHF₂ H F H H H I 2094. CHF₂ H F H H H Br 2095. CHF₂ H Br H H H Br 2096. CHF₂ H Cl H H H Me 2097. CHF₂ H Cl H H H OCHF₂ 2098. CHF₂ H Cl H H H OMe 2099. CHF₂ H Me H H H OMe 2100. CHF₂ H OEt H H H CF₃ 2101. CHF₂ H OC(O)Me H H H H 2102. CHF₂ H OEt H H H Me 2103. CHF₂ H Me Me H H Me 2104. CHF₂ H Cl H H H C(O)OMe 2105. CHF₂ H Cl H H OMe H 2106. CHF₂ H F F H F F 2107. CHF₂ H Cl H H F H 2108. CHF₂ H F H H F Cl 2109. CHF₂ H F H H Cl H 2110. CHF₂ H Cl H H CF₃ H 2111. CHF₂ H Cl Me H H H 2112. CHF₂ H OCHF₂ H H H H 2113. CHF₂ H OCH₂CF₃ H H H H 2114. CHF₂ H CF₃ H H H OCHF₂ 2115. CHF₂ H CF₃ H H H OCH₂CF₃ 2116. CHF₂ H Me H H H Me 2117. CHF₂ H Cl H H H F 2118. CHF₂ H F H F H H 2119. CHF₂ H F Me H H Cl 2120. CHF₂ H F H H OMe H 2121. CHF₂ H Cl H OCH₂O H 2122. CHF₂ H Me H H F H 2123. CHF₂ H OCF₃ H H H H 2124. CHF₂ H F F H H H 2125. CHF₂ H OMe H H Cl H 2126. Cl Cl H H H H H 2127. Cl Cl F H H H H 2128. Cl Cl F H H F H 2129. Cl Cl F H H H F 2130. Cl Cl F Me H H F 2131. Cl Cl F H H H Cl 2132. Cl Cl CF₃ H H H H 2133. Cl Cl Me H H H H 2134. Cl Cl F H H H CF₃ 2135. Cl Cl F CF₃ H H F 2136. Cl Cl Br H H H H 2137. Cl Cl I H H H H 2138. Cl Cl Cl H H H H 2139. Cl Cl Cl H Cl H H 2140. Cl Cl Cl H H H Cl 2141. Cl Cl H Cl Cl H H 2142. Cl Cl Cl Cl Cl H H 2143. Cl Cl Cl Cl H Cl H 2144. Cl Cl Cl Cl Cl H Cl 2145. Cl Cl Cl Cl Cl Cl H 2146. Cl Cl Cl Cl Cl Cl Cl 2147. Cl Cl Cl Cl H H Cl 2148. Cl Cl Cl H Cl Cl H 2149. Cl Cl Cl H H Cl Cl 2150. Cl Cl H Cl Cl Cl H 2151. Cl Cl NO₂ H H H H 2152. Cl Cl H Cl H H H 2153. Cl Cl H H Cl H H 2154. Cl Cl Cl H Cl H Cl 2155. Cl Cl Cl Cl H H H 2156. Cl Cl Cl H H Cl H 2157. Cl Cl H Cl H Cl H 2158. Cl Cl H OMe H H H 2159. Cl Cl C(O)OMe H H H H 2160. Cl Cl F Cl H H H 2161. Cl Cl F Me H H H 2162. Cl Cl H Me H H H 2163. Cl Cl OMe H H H H 2164. Cl Cl F F F H H 2165. Cl Cl F F H F H 2166. Cl Cl H F F F H 2167. Cl Cl F H F F H 2168. Cl Cl Me H Me H H 2169. Cl Cl Me H H Me H 2170. Cl Cl F H H CF₃ H 2171. Cl Cl F H Br H H 2172. Cl Cl Me Me H H H 2173. Cl Cl F F F F F 2174. Cl Cl F H H H OMe 2175. Cl Cl Cl H F H H 2176. Cl Cl NO₂ H Cl H H 2177. Cl Cl NO₂ H H Me H 2178. Cl Cl F H H H I 2179. Cl Cl F H H H Br 2180. Cl Cl Br H H H Br 2181. Cl Cl Cl H H H Me 2182. Cl Cl Cl H H H OCHF₂ 2183. Cl Cl Cl H H H OMe 2184. Cl Cl Me H H H OMe 2185. Cl Cl OEt H H H CF₃ 2186. Cl Cl OC(O)Me H H H H 2187. Cl Cl OEt H H H Me 2188. Cl Cl Me Me H H Me 2189. Cl Cl Cl H H H C(O)OMe 2190. Cl Cl Cl H H OMe H 2191. Cl Cl F F H F F 2192. Cl Cl Cl H H F H 2193. Cl Cl F H H F Cl 2194. Cl Cl F H H Cl H 2195. Cl Cl Cl H H CF₃ H 2196. Cl Cl Cl Me H H H 2197. Cl Cl OCHF₂ H H H H 2198. Cl Cl OCH₂CF₃ H H H H 2199. Cl Cl CF₃ H H H OCHF₂ 2200. Cl Cl CF₃ H H H OCH₂CF₃ 2201. Cl Cl Me H H H Me 2202. Cl Cl Cl H H H F 2203. Cl Cl F H F H H 2204. Cl Cl F Me H H Cl 2205. Cl Cl F H H OMe H 2206. Cl Cl Cl H OCH₂O H 2207. Cl Cl Me H H F H 2208. Cl Cl OCF₃ H H H H 2209. Cl Cl F F H H H 2210. Cl Cl OMe H H Cl H 2211. Me Cl H H H H H 2212. Me Cl F H H H H 2213. Me Cl F H H F H 2214. Me Cl F H H H F 2215. Me Cl F Me H H F 2216. Me Cl F H H H Cl 2217. Me Cl CF₃ H H H H 2218. Me Cl Me H H H H 2219. Me Cl F H H H CF₃ 2220. Me Cl F CF₃ H H F 2221. Me Cl Br H H H H 2222. Me Cl I H H H H 2223. Me Cl Cl H H H H 2224. Me Cl Cl H Cl H H 2225. Me Cl Cl H H H Cl 2226. Me Cl H Cl Cl H H 2227. Me Cl Cl Cl Cl H H 2228. Me Cl Cl Cl H Cl H 2229. Me Cl Cl Cl Cl H Cl 2230. Me Cl Cl Cl Cl Cl H 2231. Me Cl Cl Cl Cl Cl Cl 2232. Me Cl Cl Cl H H Cl 2233. Me Cl Cl H Cl Cl H 2234. Me Cl Cl H H Cl Cl 2235. Me Cl H Cl Cl Cl H 2236. Me Cl NO₂ H H H H 2237. Me Cl H Cl H H H 2238. Me Cl H H Cl H H 2239. Me Cl Cl H Cl H Cl 2240. Me Cl Cl Cl H H H 2241. Me Cl Cl H H Cl H 2242. Me Cl H Cl H Cl H 2243. Me Cl H OMe H H H 2244. Me Cl C(O)OMe H H H H 2245. Me Cl F Cl H H H 2246. Me Cl F Me H H H 2247. Me Cl H Me H H H 2248. Me Cl OMe H H H H 2249. Me Cl F F F H H 2250. Me Cl F F H F H 2251. Me Cl H F F F H 2252. Me Cl F H F F H 2253. Me Cl Me H Me H H 2254. Me Cl Me H H Me H 2255. Me Cl F H H CF₃ H 2256. Me Cl F H Br H H 2257. Me Cl Me Me H H H 2258. Me Cl F F F F F 2259. Me Cl F H H H OMe 2260. Me Cl Cl H F H H 2261. Me Cl NO₂ H Cl H H 2262. Me Cl NO₂ H H Me H 2263. Me Cl F H H H I 2264. Me Cl F H H H Br 2265. Me Cl Br H H H Br 2266. Me Cl Cl H H H Me 2267. Me Cl Cl H H H OCHF₂ 2268. Me Cl Cl H H H OMe 2269. Me Cl Me H H H OMe 2270. Me Cl OEt H H H CF₃ 2271. Me Cl OC(O)Me H H H H 2272. Me Cl OEt H H H Me 2273. Me Cl Me Me H H Me 2274. Me Cl Cl H H H C(O)OMe 2275. Me Cl Cl H H OMe H 2276. Me Cl F F H F F 2277. Me Cl Cl H H F H 2278. Me Cl F H H F Cl 2279. Me Cl F H H Cl H 2280. Me Cl Cl H H CF₃ H 2281. Me Cl Cl Me H H H 2282. Me Cl OCHF₂ H H H H 2283. Me Cl OCH₂CF₃ H H H H 2284. Me Cl CF₃ H H H OCHF₂ 2285. Me Cl CF₃ H H H OCH₂CF₃ 2286. Me Cl Me H H H Me 2287. Me Cl Cl H H H F 2288. Me Cl F H F H H 2289. Me Cl F Me H H Cl 2290. Me Cl F H H OMe H 2291. Me Cl Cl H OCH₂O H 2292. Me Cl Me H H F H 2293. Me Cl OCF₃ H H H H 2294. Me Cl F F H H H 2295. Me Cl OMe H H Cl H 2296. Cl Me H H H H H 2297. Cl Me F H H H H 2298. Cl Me F H H F H 2299. Cl Me F H H H F 2300. Cl Me F Me H H F 2301. Cl Me F H H H Cl 2302. Cl Me CF₃ H H H H 2303. Cl Me Me H H H H 2304. Cl Me F H H H CF₃ 2305. Cl Me F CF₃ H H F 2306. Cl Me Br H H H H 2307. Cl Me I H H H H 2308. Cl Me Cl H H H H 2309. Cl Me Cl H Cl H H 2310. Cl Me Cl H H H Cl 2311. Cl Me H Cl Cl H H 2312. Cl Me Cl Cl Cl H H 2313. Cl Me Cl Cl H Cl H 2314. Cl Me Cl Cl Cl H Cl 2315. Cl Me Cl Cl Cl Cl H 2316. Cl Me Cl Cl Cl Cl Cl 2317. Cl Me Cl Cl H H Cl 2318. Cl Me Cl H Cl Cl H 2319. Cl Me Cl H H Cl Cl 2320. Cl Me H Cl Cl Cl H 2321. Cl Me NO₂ H H H H 2322. Cl Me H Cl H H H 2323. Cl Me H H Cl H H 2324. Cl Me Cl H Cl H Cl 2325. Cl Me Cl Cl H H H 2326. Cl Me Cl H H Cl H 2327. Cl Me H Cl H Cl H 2328. Cl Me H OMe H H H 2329. Cl Me C(O)OMe H H H H 2330. Cl Me F Cl H H H 2331. Cl Me F Me H H H 2332. Cl Me H Me H H H 2333. Cl Me OMe H H H H 2334. Cl Me F F F H H 2335. Cl Me F F H F H 2336. Cl Me H F F F H 2337. Cl Me F H F F H 2338. Cl Me Me H Me H H 2339. Cl Me Me H H Me H 2340. Cl Me F H H CF₃ H 2341. Cl Me F H Br H H 2342. Cl Me Me Me H H H 2343. Cl Me F F F F F 2344. Cl Me F H H H OMe 2345. Cl Me Cl H F H H 2346. Cl Me NO₂ H Cl H H 2347. Cl Me NO₂ H H Me H 2348. Cl Me F H H H I 2349. Cl Me F H H H Br 2350. Cl Me Br H H H Br 2351. Cl Me Cl H H H Me 2352. Cl Me Cl H H H OCHF₂ 2353. Cl Me Cl H H H OMe 2354. Cl Me Me H H H OMe 2355. Cl Me OEt H H H CF₃ 2356. Cl Me OC(O)Me H H H H 2357. Cl Me OEt H H H Me 2358. Cl Me Me Me H H Me 2359. Cl Me Cl H H H C(O)OMe 2360. Cl Me Cl H H OMe H 2361. Cl Me F F H F F 2362. Cl Me Cl H H F H 2363. Cl Me F H H F Cl 2364. Cl Me F H H Cl H 2365. Cl Me Cl H H CF₃ H 2366. Cl Me Cl Me H H H 2367. Cl Me OCHF₂ H H H H 2368. Cl Me OCH₂CF₃ H H H H 2369. Cl Me CF₃ H H H OCHF₂ 2370. Cl Me CF₃ H H H OCH₂CF₃ 2371. Cl Me Me H H H Me 2372. Cl Me Cl H H H F 2373. Cl Me F H F H H 2374. Cl Me F Me H H Cl 2375. Cl Me F H H OMe H 2376. Cl Me Cl H OCH₂O H 2377. Cl Me Me H H F H 2378. Cl Me OCF₃ H H H H 2379. Cl Me F F H H H 2380. Cl Me OMe H H Cl H

TABLE 3 Compounds of the formula Ib-S (Ib-S)

Ex. No. R¹¹ R¹² R⁶ R⁷ R⁸ 2381. H H CF₃ Ph Cl 2382. H H CF₃ ^(t)Bu Cl 2383. H H CF₃ CHF₂ Cl 2384. H H Cl CHF₂ CF₃ 2385. H H CF₃ Me OMe 2386. H H CF₃ Me CN 2387. H H Cl Et Cl 2388. H H CHF₂ Me Cl 2389. H H Me Me Me 2390. H H Me Me Cl 2391. H H Cl Me Cl 2392. H H CF₃ Me Cl 2393. H H Cl Me CF₃ 2394. H H CF₃ Me F 2395. H H OMe Me CF₃ 2396. H H CF₃ Me OEt 2397. H H CF₃ Me OCHF₂ 2398. H H OCHF₂ Me CF₃ 2399. H H CF₃ Me OCH₂CHF₂ 2400. H H CF₃ Me OCH₂CF₃ 2401. H H CF₃ Me OCH₂CN 2402. H H CF₃ Me SO₂Me 2403. H H CF₃ Me SEt 2404. H H CF₃ Me Me 2405. H H CF₃ Me Et 2406. H H CF₃ Et Cl 2407. H H Cl Et CF₃ 2408. H H CF₃ ^(i)Pr Cl 2409. H H Cl ^(i)Pr CF₃ 2410. H H CF₃ ^(t)Bu Cl 2411. H H Cl ^(t)Bu CF₃ 2412. H H CF₃ cPen Cl 2413. H H Cl cPen CF₃ 2414. H H CF₃ CH₂cPr Cl 2415. H H Cl CH₂cPr CF₃ 2416. H H CF₃ CH₂CH═CH₂ Cl 2417. H H Cl CH₂CH═CH₂ CF₃ 2418. H H CF₃ CHF₂ OMe 2419. H H OMe CHF₂ CF₃ 2420. H H CF₃ CH₂CF₃ Cl 2421. H H Cl CH₂CF₃ CF₃ 2422. H H CF₃ CH₂OMe Cl 2423. H H Cl CH₂OMe CF₃ 2424. H H CF₃ CH₂CN Cl 2425. H H Me Ph Me 2426. H H Me Ph Cl 2427. H H Et Ph Cl 2428. H H Pr Ph Cl 2429. H H ^(i)Pr Ph Cl 2430. H H CF₃ Ph Cl 2431. H H CF₃ Ph Me 2432. H H CF₃ Ph CF₃ 2433. H H CF₃ Ph F 2434. H H CF₃ Ph OMe 2435. H H CF₃ Ph OEt 2436. H H CF₃ Ph OCHF₂ 2437. H H CF₃ Ph CN 2438. H H CF₃ Ph(4-Cl) Cl 2439. H H Me Me OCH₂CF₃ 2440. H H CF₃ Me

2441. H H CF₃ Me H 2442. H H CF₃ Me OCH₂CH₂OMe 2443. H H CF₃ Me SMe 2444. H H CF₃ Me OCH₂CH₂CH₂F 2445. H H CF₃ Me OCH(CH₂F)₂ 2446. H H CF₃ Me OCH₂CF₂CHF₂ 2447. H H CF₃ Me OCH₂CF═CH₂ 2448. H H CF₃ Me OCH(Me)CF₃ 2449. H H CF₃ Me OCH(Me)CH₂F 2450. H H OCH₂CF₃ Me CF₃ 2451. H H OCH₂CF₃ Me CHF₂ 2452. H H CHF₂ Me CHF₂ 2453. H H CF₃ Me CHF₂ 2454. H H Cl Me OCHF₂ 2455. H H Br Me OCHF₂ 2456. H H Br Me CF₃ 2457. F H CF₃ Ph Cl 2458. F H CF₃ ^(t)Bu Cl 2459. F H CF₃ CHF₂ Cl 2460. F H Cl CHF₂ CF₃ 2461. F H CF₃ Me OMe 2462. F H CF₃ Me CN 2463. F H Cl Et Cl 2464. F H CHF₂ Me Cl 2465. F H Me Me Me 2466. F H Me Me Cl 2467. F H Cl Me Cl 2468. F H CF₃ Me Cl 2469. F H Cl Me CF₃ 2470. F H CF₃ Me F 2471. F H OMe Me CF₃ 2472. F H CF₃ Me OEt 2473. F H CF₃ Me OCHF₂ 2474. F H OCHF₂ Me CF₃ 2475. F H CF₃ Me OCH₂CHF₂ 2476. F H CF₃ Me OCH₂CF₃ 2477. F H CF₃ Me OCH₂CN 2478. F H CF₃ Me SO₂Me 2479. F H CF₃ Me SEt 2480. F H CF₃ Me Me 2481. F H CF₃ Me Et 2482. F H CF₃ Et Cl 2483. F H Cl Et CF₃ 2484. F H CF₃ ^(i)Pr Cl 2485. F H Cl ^(i)Pr CF₃ 2486. F H CF₃ ^(t)Bu Cl 2487. F H Cl ^(t)Bu CF₃ 2488. F H CF₃ cPen Cl 2489. F H Cl cPen CF₃ 2490. F H CF₃ CH₂cPr Cl 2491. F H Cl CH₂cPr CF₃ 2492. F H CF₃ CH₂CH═CH₂ Cl 2493. F H Cl CH₂CH═CH₂ CF₃ 2494. F H CF₃ CHF₂ OMe 2495. F H OMe CHF₂ CF₃ 2496. F H CF₃ CH₂CF₃ Cl 2497. F H Cl CH₂CF₃ CF₃ 2498. F H CF₃ CH₂OMe Cl 2499. F H Cl CH₂OMe CF₃ 2500. F H CF₃ CH₂CN Cl 2501. F H Me Ph Me 2502. F H Me Ph Cl 2503. F H Et Ph Cl 2504. F H Pr Ph Cl 2505. F H ^(i)Pr Ph Cl 2506. F H CF₃ Ph Cl 2507. F H CF₃ Ph Me 2508. F H CF₃ Ph CF₃ 2509. F H CF₃ Ph F 2510. F H CF₃ Ph OMe 2511. F H CF₃ Ph OEt 2512. F H CF₃ Ph OCHF₂ 2513. F H CF₃ Ph CN 2514. F H CF₃ Ph(4-Cl) Cl 2515. F H Me Me OCH₂CF₃ 2516. F H CF₃ Me

2517. F H CF₃ Me H 2518. F H CF₃ Me OCH₂CH₂OMe 2519. F H CF₃ Me SMe 2520. F H CF₃ Me OCH₂CH₂CH₂F 2521. F H CF₃ Me OCH(CH₂F)₂ 2522. F H CF₃ Me OCH₂CF₂CHF₂ 2523. F H CF₃ Me OCH₂CF═CH₂ 2524. F H CF₃ Me OCH(Me)CF₃ 2525. F H CF₃ Me OCH(Me)CH₂F 2526. F H OCH₂CF₃ Me CF₃ 2527. F H OCH₂CF₃ Me CHF₂ 2528. F H CHF₂ Me CHF₂ 2529. F H CF₃ Me CHF₂ 2530. F H Cl Me OCHF₂ 2531. F H Br Me OCHF₂ 2532. F H Br Me CF₃ 2533. F H CF₃ Me CF₃ 2534. F H CHF₂ Me OCHF₂ 2535. F H CHF₂ Me CF₃ 2536. F H CF₂CF₃ Me CF₃ 2537. F H CF₃ Me CF₂CF₃ 2538. F H CHF₂ Me OCH₂CF₃ 2539. Cl H CF₃ Ph Cl 2540. Cl H CF₃ ^(t)Bu Cl 2541. Cl H CF₃ CHF₂ Cl 2542. Cl H Cl CHF₂ CF₃ 2543. Cl H CF₃ Me OMe 2544. Cl H CF₃ Me CN 2545. Cl H Cl Et Cl 2546. Cl H CHF₂ Me Cl 2547. Cl H Me Me Me 2548. Cl H Me Me Cl 2549. Cl H Cl Me Cl 2550. Cl H CF₃ Me Cl 2551. Cl H Cl Me CF₃ 2552. Cl H CF₃ Me F 2553. Cl H OMe Me CF₃ 2554. Cl H CF₃ Me OEt 2555. Cl H CF₃ Me OCHF₂ 2556. Cl H OCHF₂ Me CF₃ 2557. Cl H CF₃ Me OCH₂CHF₂ 2558. Cl H CF₃ Me OCH₂CF₃ 2559. Cl H CF₃ Me OCH₂CN 2560. Cl H CF₃ Me SO₂Me 2561. Cl H CF₃ Me SEt 2562. Cl H CF₃ Me Me 2563. Cl H CF₃ Me Et 2564. Cl H CF₃ Et Cl 2565. Cl H Cl Et CF₃ 2566. Cl H CF₃ ^(i)Pr Cl 2567. Cl H Cl ^(i)Pr CF₃ 2568. Cl H CF₃ ^(t)Bu Cl 2569. Cl H Cl ^(t)Bu CF₃ 2570. Cl H CF₃ cPen Cl 2571. Cl H Cl cPen CF₃ 2572. Cl H CF₃ CH₂cPr Cl 2573. Cl H Cl CH₂cPr CF₃ 2574. Cl H CF₃ CH₂CH═CH₂ Cl 2575. Cl H Cl CH₂CH═CH₂ CF₃ 2576. Cl H CF₃ CHF₂ OMe 2577. Cl H OMe CHF₂ CF₃ 2578. Cl H CF₃ CH₂CF₃ Cl 2579. Cl H Cl CH₂CF₃ CF₃ 2580. Cl H CF₃ CH₂OMe Cl 2581. Cl H Cl CH₂OMe CF₃ 2582. Cl H CF₃ CH₂CN Cl 2583. Cl H Me Ph Me 2584. Cl H Me Ph Cl 2585. Cl H Et Ph Cl 2586. Cl H Pr Ph Cl 2587. Cl H ^(i)Pr Ph Cl 2588. Cl H CF₃ Ph Cl 2589. Cl H CF₃ Ph Me 2590. Cl H CF₃ Ph CF₃ 2591. Cl H CF₃ Ph F 2592. Cl H CF₃ Ph OMe 2593. Cl H CF₃ Ph OEt 2594. Cl H CF₃ Ph OCHF₂ 2595. Cl H CF₃ Ph CN 2596. Cl H CF₃ Ph(4-Cl) Cl 2597. Cl H Me Me OCH₂CF₃ 2598. Cl H CF₃ Me

2599. Cl H CF₃ Me H 2600. Cl H CF₃ Me OCH₂CH₂OMe 2601. Cl H CF₃ Me SMe 2602. Cl H CF₃ Me OCH₂CH₂CH₂F 2603. Cl H CF₃ Me OCH(CH₂F)₂ 2604. Cl H CF₃ Me OCH₂CF₂CHF₂ 2605. Cl H CF₃ Me OCH₂CF═CH₂ 2606. Cl H CF₃ Me OCH(Me)CF₃ 2607. Cl H CF₃ Me OCH(Me)CH₂F 2608. Cl H OCH₂CF₃ Me CF₃ 2609. Cl H OCH₂CF₃ Me CHF₂ 2610. Cl H CHF₂ Me CHF₂ 2611. Cl H CF₃ Me CHF₂ 2612. Cl H Cl Me OCHF₂ 2613. Cl H Br Me OCHF₂ 2614. Cl H Br Me CF₃ 2615. Cl H CF₃ Me CF₃ 2616. Cl H CHF₂ Me OCHF₂ 2617. Cl H CHF₂ Me CF₃ 2618. Cl H CF₂CF₃ Me CF₃ 2619. Cl H CF₃ Me CF₂CF₃ 2620. Cl H CHF₂ Me OCH₂CF₃ 2621. Br H CF₃ Ph Cl 2622. Br H CF₃ ^(t)Bu Cl 2623. Br H CF₃ CHF₂ Cl 2624. Br H Cl CHF₂ CF₃ 2625. Br H CF₃ Me OMe 2626. Br H CF₃ Me CN 2627. Br H Cl Et Cl 2628. Br H CHF₂ Me Cl 2629. Br H Me Me Me 2630. Br H Me Me Cl 2631. Br H Cl Me Cl 2632. Br H CF₃ Me Cl 2633. Br H Cl Me CF₃ 2634. Br H CF₃ Me F 2635. Br H OMe Me CF₃ 2636. Br H CF₃ Me OEt 2637. Br H CF₃ Me OCHF₂ 2638. Br H OCHF₂ Me CF₃ 2639. Br H CF₃ Me OCH₂CHF₂ 2640. Br H CF₃ Me OCH₂CF₃ 2641. Br H CF₃ Me OCH₂CN 2642. Br H CF₃ Me SO₂Me 2643. Br H CF₃ Me SEt 2644. Br H CF₃ Me Me 2645. Br H CF₃ Me Et 2646. Br H CF₃ Et Cl 2647. Br H Cl Et CF₃ 2648. Br H CF₃ ^(i)Pr Cl 2649. Br H Cl ^(i)Pr CF₃ 2650. Br H CF₃ ^(t)Bu Cl 2651. Br H Cl ^(t)Bu CF₃ 2652. Br H CF₃ cPen Cl 2653. Br H Cl cPen CF₃ 2654. Br H CF₃ CH₂cPr Cl 2655. Br H Cl CH₂cPr CF₃ 2656. Br H CF₃ CH₂CH═CH₂ Cl 2657. Br H Cl CH₂CH═CH₂ CF₃ 2658. Br H CF₃ CHF₂ OMe 2659. Br H OMe CHF₂ CF₃ 2660. Br H CF₃ CH₂CF₃ Cl 2661. Br H Cl CH₂CF₃ CF₃ 2662. Br H CF₃ CH₂OMe Cl 2663. Br H Cl CH₂OMe CF₃ 2664. Br H CF₃ CH₂CN Cl 2665. Br H Me Ph Me 2666. Br H Me Ph Cl 2667. Br H Et Ph Cl 2668. Br H Pr Ph Cl 2669. Br H ^(i)Pr Ph Cl 2670. Br H CF₃ Ph Cl 2671. Br H CF₃ Ph Me 2672. Br H CF₃ Ph CF₃ 2673. Br H CF₃ Ph F 2674. Br H CF₃ Ph OMe 2675. Br H CF₃ Ph OEt 2676. Br H CF₃ Ph OCHF₂ 2677. Br H CF₃ Ph CN 2678. Br H CF₃ Ph(4-Cl) Cl 2679. Br H Me Me OCH₂CF₃ 2680. Br H CF₃ Me

2681. Br H CF₃ Me H 2682. Br H CF₃ Me OCH₂CH₂OMe 2683. Br H CF₃ Me SMe 2684. Br H CF₃ Me OCH₂CH₂CH₂F 2685. Br H CF₃ Me OCH(CH₂F)₂ 2686. Br H CF₃ Me OCH₂CF₂CHF₂ 2687. Br H CF₃ Me OCH₂CF═CH₂ 2688. Br H CF₃ Me OCH(Me)CF₃ 2689. Br H CF₃ Me OCH(Me)CH₂F 2690. Br H OCH₂CF₃ Me CF₃ 2691. Br H OCH₂CF₃ Me CHF₂ 2692. Br H CHF₂ Me CHF₂ 2693. Br H CF₃ Me CHF₂ 2694. Br H Cl Me OCHF₂ 2695. Br H Br Me OCHF₂ 2696. Br H Br Me CF₃ 2697. Br H CF₃ Me CF₃ 2698. Br H CHF₂ Me OCHF₂ 2699. Br H CHF₂ Me CF₃ 2700. Br H CF₂CF₃ Me CF₃ 2701. Br H CF₃ Me CF₂CF₃ 2702. Br H CHF₂ Me OCH₂CF₃ 2703. I H CF₃ Ph Cl 2704. I H CF₃ ^(t)Bu Cl 2705. I H CF₃ CHF₂ Cl 2706. I H Cl CHF₂ CF₃ 2707. I H CF₃ Me OMe 2708. I H CF₃ Me CN 2709. I H Cl Et Cl 2710. I H CHF₂ Me Cl 2711. I H Me Me Me 2712. I H Me Me Cl 2713. I H Cl Me Cl 2714. I H CF₃ Me Cl 2715. I H Cl Me CF₃ 2716. I H CF₃ Me F 2717. I H OMe Me CF₃ 2718. I H CF₃ Me OEt 2719. I H CF₃ Me OCHF₂ 2720. I H OCHF₂ Me CF₃ 2721. I H CF₃ Me OCH₂CHF₂ 2722. I H CF₃ Me OCH₂CF₃ 2723. I H CF₃ Me OCH₂CN 2724. I H CF₃ Me SO₂Me 2725. I H CF₃ Me SEt 2726. I H CF₃ Me Me 2727. I H CF₃ Me Et 2728. I H CF₃ Et Cl 2729. I H Cl Et CF₃ 2730. I H CF₃ ^(i)Pr Cl 2731. I H Cl ^(i)Pr CF₃ 2732. I H CF₃ ^(t)Bu Cl 2733. I H Cl ^(t)Bu CF₃ 2734. I H CF₃ cPen Cl 2735. I H Cl cPen CF₃ 2736. I H CF₃ CH₂cPr Cl 2737. I H Cl CH₂cPr CF₃ 2738. I H CF₃ CH₂CH═CH₂ Cl 2739. I H Cl CH₂CH═CH₂ CF₃ 2740. I H CF₃ CHF₂ OMe 2741. I H OMe CHF₂ CF₃ 2742. I H CF₃ CH₂CF₃ Cl 2743. I H Cl CH₂CF₃ CF₃ 2744. I H CF₃ CH₂OMe Cl 2745. I H Cl CH₂OMe CF₃ 2746. I H CF₃ CH₂CN Cl 2747. I H Me Ph Me 2748. I H Me Ph Cl 2749. I H Et Ph Cl 2750. I H Pr Ph Cl 2751. I H ^(i)Pr Ph Cl 2752. I H CF₃ Ph Cl 2753. I H CF₃ Ph Me 2754. I H CF₃ Ph CF₃ 2755. I H CF₃ Ph F 2756. I H CF₃ Ph OMe 2757. I H CF₃ Ph OEt 2758. I H CF₃ Ph OCHF₂ 2759. I H CF₃ Ph CN 2760. I H CF₃ Ph(4-Cl) Cl 2761. I H Me Me OCH₂CF₃ 2762. I H CF₃ Me

2763. I H CF₃ Me H 2764. I H CF₃ Me OCH₂CH₂OMe 2765. I H CF₃ Me SMe 2766. I H CF₃ Me OCH₂CH₂CH₂F 2767. I H CF₃ Me OCH(CH₂F)₂ 2768. I H CF₃ Me OCH₂CF₂CHF₂ 2769. I H CF₃ Me OCH₂CF═CH₂ 2770. I H CF₃ Me OCH(Me)CF₃ 2771. I H CF₃ Me OCH(Me)CH₂F 2772. I H OCH₂CF₃ Me CF₃ 2773. I H OCH₂CF₃ Me CHF₂ 2774. I H CHF₂ Me CHF₂ 2775. I H CF₃ Me CHF₂ 2776. I H Cl Me OCHF₂ 2777. I H Br Me OCHF₂ 2778. I H Br Me CF₃ 2779. I H CF₃ Me CF₃ 2780. I H CHF₂ Me OCHF₂ 2781. I H CHF₂ Me CF₃ 2782. I H CF₂CF₃ Me CF₃ 2783. I H CF₃ Me CF₂CF₃ 2784. I H CHF₂ Me OCH₂CF₃ 2785. H Cl CF₃ Ph Cl 2786. H Cl CF₃ ^(t)Bu Cl 2787. H Cl CF₃ CHF₂ Cl 2788. H Cl Cl CHF₂ CF₃ 2789. H Cl CF₃ Me OMe 2790. H Cl CF₃ Me CN 2791. H Cl Cl Et Cl 2792. H Cl CHF₂ Me Cl 2793. H Cl Me Me Me 2794. H Cl Me Me Cl 2795. H Cl Cl Me Cl 2796. H Cl CF₃ Me Cl 2797. H Cl Cl Me CF₃ 2798. H Cl CF₃ Me F 2799. H Cl OMe Me CF₃ 2800. H Cl CF₃ Me OEt 2801. H Cl CF₃ Me OCHF₂ 2802. H Cl OCHF₂ Me CF₃ 2803. H Cl CF₃ Me OCH₂CHF₂ 2804. H Cl CF₃ Me OCH₂CF₃ 2805. H Cl CF₃ Me OCH₂CN 2806. H Cl CF₃ Me SO₂Me 2807. H Cl CF₃ Me SEt 2808. H Cl CF₃ Me Me 2809. H Cl CF₃ Me Et 2810. H Cl CF₃ Et Cl 2811. H Cl Cl Et CF₃ 2812. H Cl CF₃ ^(i)Pr Cl 2813. H Cl Cl ^(i)Pr CF₃ 2814. H Cl CF₃ ^(t)Bu Cl 2815. H Cl Cl ^(t)Bu CF₃ 2816. H Cl CF₃ cPen Cl 2817. H Cl Cl cPen CF₃ 2818. H Cl CF₃ CH₂cPr Cl 2819. H Cl Cl CH₂cPr CF₃ 2820. H Cl CF₃ CH₂CH═CH₂ Cl 2821. H Cl Cl CH₂CH═CH₂ CF₃ 2822. H Cl CF₃ CHF₂ OMe 2823. H Cl OMe CHF₂ CF₃ 2824. H Cl CF₃ CH₂CF₃ Cl 2825. H Cl Cl CH₂CF₃ CF₃ 2826. H Cl CF₃ CH₂OMe Cl 2827. H Cl Cl CH₂OMe CF₃ 2828. H Cl CF₃ CH₂CN Cl 2829. H Cl Me Ph Me 2830. H Cl Me Ph Cl 2831. H Cl Et Ph Cl 2832. H Cl Pr Ph Cl 2833. H Cl ^(i)Pr Ph Cl 2834. H Cl CF₃ Ph Cl 2835. H Cl CF₃ Ph Me 2836. H Cl CF₃ Ph CF₃ 2837. H Cl CF₃ Ph F 2838. H Cl CF₃ Ph OMe 2839. H Cl CF₃ Ph OEt 2840. H Cl CF₃ Ph OCHF₂ 2841. H Cl CF₃ Ph CN 2842. H Cl CF₃ Ph(4-Cl) Cl 2843. H Cl Me Me OCH₂CF₃ 2844. H Cl CF₃ Me

2845. H Cl CF₃ Me H 2846. H Cl CF₃ Me OCH₂CH₂OMe 2847. H Cl CF₃ Me SMe 2848. H Cl CF₃ Me OCH₂CH₂CH₂F 2849. H Cl CF₃ Me OCH(CH₂F)₂ 2850. H Cl CF₃ Me OCH₂CF₂CHF₂ 2851. H Cl CF₃ Me OCH₂CF═CH₂ 2852. H Cl CF₃ Me OCH(Me)CF₃ 2853. H Cl CF₃ Me OCH(Me)CH₂F 2854. H Cl OCH₂CF₃ Me CF₃ 2855. H Cl OCH₂CF₃ Me CHF₂ 2856. H Cl CHF₂ Me CHF₂ 2857. H Cl CF₃ Me CHF₂ 2858. H Cl Cl Me OCHF₂ 2859. H Cl Br Me OCHF₂ 2860. H Cl Br Me CF₃ 2861. H Br CF₃ Ph Cl 2862. H Br CF₃ ^(t)Bu Cl 2863. H Br CF₃ CHF₂ Cl 2864. H Br Cl CHF₂ CF₃ 2865. H Br CF₃ Me OMe 2866. H Br CF₃ Me CN 2867. H Br Cl Et Cl 2868. H Br CHF₂ Me Cl 2869. H Br Me Me Me 2870. H Br Me Me Cl 2871. H Br Cl Me Cl 2872. H Br CF₃ Me Cl 2873. H Br Cl Me CF₃ 2874. H Br CF₃ Me F 2875. H Br OMe Me CF₃ 2876. H Br CF₃ Me OEt 2877. H Br CF₃ Me OCHF₂ 2878. H Br OCHF₂ Me CF₃ 2879. H Br CF₃ Me OCH₂CHF₂ 2880. H Br CF₃ Me OCH₂CF₃ 2881. H Br CF₃ Me OCH₂CN 2882. H Br CF₃ Me SO₂Me 2883. H Br CF₃ Me SEt 2884. H Br CF₃ Me Me 2885. H Br CF₃ Me Et 2886. H Br CF₃ Et Cl 2887. H Br Cl Et CF₃ 2888. H Br CF₃ ^(i)Pr Cl 2889. H Br Cl ^(i)Pr CF₃ 2890. H Br CF₃ ^(t)Bu Cl 2891. H Br Cl ^(t)Bu CF₃ 2892. H Br CF₃ cPen Cl 2893. H Br Cl cPen CF₃ 2894. H Br CF₃ CH₂cPr Cl 2895. H Br Cl CH₂cPr CF₃ 2896. H Br CF₃ CH₂CH═CH₂ Cl 2897. H Br Cl CH₂CH═CH₂ CF₃ 2898. H Br CF₃ CHF₂ OMe 2899. H Br OMe CHF₂ CF₃ 2900. H Br CF₃ CH₂CF₃ Cl 2901. H Br Cl CH₂CF₃ CF₃ 2902. H Br CF₃ CH₂OMe Cl 2903. H Br Cl CH₂OMe CF₃ 2904. H Br CF₃ CH₂CN Cl 2905. H Br Me Ph Me 2906. H Br Me Ph Cl 2907. H Br Et Ph Cl 2908. H Br Pr Ph Cl 2909. H Br ^(i)Pr Ph Cl 2910. H Br CF₃ Ph Cl 2911. H Br CF₃ Ph Me 2912. H Br CF₃ Ph CF₃ 2913. H Br CF₃ Ph F 2914. H Br CF₃ Ph OMe 2915. H Br CF₃ Ph OEt 2916. H Br CF₃ Ph OCHF₂ 2917. H Br CF₃ Ph CN 2918. H Br CF₃ Ph(4-Cl) Cl 2919. H Br Me Me OCH₂CF₃ 2920. H Br CF₃ Me

2921. H Br CF₃ Me H 2922. H Br CF₃ Me OCH₂CH₂OMe 2923. H Br CF₃ Me SMe 2924. H Br CF₃ Me OCH₂CH₂CH₂F 2925. H Br CF₃ Me OCH(CH₂F)₂ 2926. H Br CF₃ Me OCH₂CF₂CHF₂ 2927. H Br CF₃ Me OCH₂CF═CH₂ 2928. H Br CF₃ Me OCH(Me)CF₃ 2929. H Br CF₃ Me OCH(Me)CH₂F 2930. H Br OCH₂CF₃ Me CF₃ 2931. H Br OCH₂CF₃ Me CHF₂ 2932. H Br CHF₂ Me CHF₂ 2933. H Br CF₃ Me CHF₂ 2934. H Br Cl Me OCHF₂ 2935. H Br Br Me OCHF₂ 2936. H Br Br Me CF₃ 2937. Me H CF₃ Ph Cl 2938. Me H CF₃ ^(t)Bu Cl 2939. Me H CF₃ CHF₂ Cl 2940. Me H Cl CHF₂ CF₃ 2941. Me H CF₃ Me OMe 2942. Me H CF₃ Me CN 2943. Me H Cl Et Cl 2944. Me H CHF₂ Me Cl 2945. Me H Me Me Me 2946. Me H Me Me Cl 2947. Me H Cl Me Cl 2948. Me H CF₃ Me Cl 2949. Me H Cl Me CF₃ 2950. Me H CF₃ Me F 2951. Me H OMe Me CF₃ 2952. Me H CF₃ Me OEt 2953. Me H CF₃ Me OCHF₂ 2954. Me H OCHF₂ Me CF₃ 2955. Me H CF₃ Me OCH₂CHF₂ 2956. Me H CF₃ Me OCH₂CF₃ 2957. Me H CF₃ Me OCH₂CN 2958. Me H CF₃ Me SO₂Me 2959. Me H CF₃ Me SEt 2960. Me H CF₃ Me Me 2961. Me H CF₃ Me Et 2962. Me H CF₃ Et Cl 2963. Me H Cl Et CF₃ 2964. Me H CF₃ ^(i)Pr Cl 2965. Me H Cl ^(i)Pr CF₃ 2966. Me H CF₃ ^(t)Bu Cl 2967. Me H Cl ^(t)Bu CF₃ 2968. Me H CF₃ cPen Cl 2969. Me H Cl cPen CF₃ 2970. Me H CF₃ CH₂cPr Cl 2971. Me H Cl CH₂cPr CF₃ 2972. Me H CF₃ CH₂CH═CH₂ Cl 2973. Me H Cl CH₂CH═CH₂ CF₃ 2974. Me H CF₃ CHF₂ OMe 2975. Me H OMe CHF₂ CF₃ 2976. Me H CF₃ CH₂CF₃ Cl 2977. Me H Cl CH₂CF₃ CF₃ 2978. Me H CF₃ CH₂OMe Cl 2979. Me H Cl CH₂OMe CF₃ 2980. Me H CF₃ CH₂CN Cl 2981. Me H Me Ph Me 2982. Me H Me Ph Cl 2983. Me H Et Ph Cl 2984. Me H Pr Ph Cl 2985. Me H ^(i)Pr Ph Cl 2986. Me H CF₃ Ph Cl 2987. Me H CF₃ Ph Me 2988. Me H CF₃ Ph CF₃ 2989. Me H CF₃ Ph F 2990. Me H CF₃ Ph OMe 2991. Me H CF₃ Ph OEt 2992. Me H CF₃ Ph OCHF₂ 2993. Me H CF₃ Ph CN 2994. Me H CF₃ Ph(4-Cl) Cl 2995. Me H Me Me OCH₂CF₃ 2996. Me H CF₃ Me

2997. Me H CF₃ Me H 2998. Me H CF₃ Me OCH₂CH₂OMe 2999. Me H CF₃ Me SMe 3000. Me H CF₃ Me OCH₂CH₂CH₂F 3001. Me H CF₃ Me OCH(CH₂F)₂ 3002. Me H CF₃ Me OCH₂CF₂CHF₂ 3003. Me H CF₃ Me OCH₂CF═CH₂ 3004. Me H CF₃ Me OCH(Me)CF₃ 3005. Me H CF₃ Me OCH(Me)CH₂F 3006. Me H OCH₂CF₃ Me CF₃ 3007. Me H OCH₂CF₃ Me CHF₂ 3008. Me H CHF₂ Me CHF₂ 3009. Me H CF₃ Me CHF₂ 3010. Me H Cl Me OCHF₂ 3011. Me H Br Me OCHF₂ 3012. Me H Br Me CF₃ 3013. H Me CF₃ Ph Cl 3014. H Me CF₃ ^(t)Bu Cl 3015. H Me CF₃ CHF₂ Cl 3016. H Me Cl CHF₂ CF₃ 3017. H Me CF₃ Me OMe 3018. H Me CF₃ Me CN 3019. H Me Cl Et Cl 3020. H Me CHF₂ Me Cl 3021. H Me Me Me Me 3022. H Me Me Me Cl 3023. H Me Cl Me Cl 3024. H Me CF₃ Me Cl 3025. H Me Cl Me CF₃ 3026. H Me CF₃ Me F 3027. H Me OMe Me CF₃ 3028. H Me CF₃ Me OEt 3029. H Me CF₃ Me OCHF₂ 3030. H Me OCHF₂ Me CF₃ 3031. H Me CF₃ Me OCH₂CHF₂ 3032. H Me CF₃ Me OCH₂CF₃ 3033. H Me CF₃ Me OCH₂CN 3034. H Me CF₃ Me SO₂Me 3035. H Me CF₃ Me SEt 3036. H Me CF₃ Me Me 3037. H Me CF₃ Me Et 3038. H Me CF₃ Et Cl 3039. H Me Cl Et CF₃ 3040. H Me CF₃ ^(i)Pr Cl 3041. H Me Cl ^(i)Pr CF₃ 3042. H Me CF₃ ^(t)Bu Cl 3043. H Me Cl ^(t)Bu CF₃ 3044. H Me CF₃ cPen Cl 3045. H Me Cl cPen CF₃ 3046. H Me CF₃ CH₂cPr Cl 3047. H Me Cl CH₂cPr CF₃ 3048. H Me CF₃ CH₂CH═CH₂ Cl 3049. H Me Cl CH₂CH═CH₂ CF₃ 3050. H Me CF₃ CHF₂ OMe 3051. H Me OMe CHF₂ CF₃ 3052. H Me CF₃ CH₂CF₃ Cl 3053. H Me Cl CH₂CF₃ CF₃ 3054. H Me CF₃ CH₂OMe Cl 3055. H Me Cl CH₂OMe CF₃ 3056. H Me CF₃ CH₂CN Cl 3057. H Me Me Ph Me 3058. H Me Me Ph Cl 3059. H Me Et Ph Cl 3060. H Me Pr Ph Cl 3061. H Me ^(i)Pr Ph Cl 3062. H Me CF₃ Ph Cl 3063. H Me CF₃ Ph Me 3064. H Me CF₃ Ph CF₃ 3065. H Me CF₃ Ph F 3066. H Me CF₃ Ph OMe 3067. H Me CF₃ Ph OEt 3068. H Me CF₃ Ph OCHF₂ 3069. H Me CF₃ Ph CN 3070. H Me CF₃ Ph(4-Cl) Cl 3071. H Me Me Me OCH₂CF₃ 3072. H Me CF₃ Me

3073. H Me CF₃ Me H 3074. H Me CF₃ Me OCH₂CH₂OMe 3075. H Me CF₃ Me SMe 3076. H Me CF₃ Me OCH₂CH₂CH₂F 3077. H Me CF₃ Me OCH(CH₂F)₂ 3078. H Me CF₃ Me OCH₂CF₂CHF₂ 3079. H Me CF₃ Me OCH₂CF═CH₂ 3080. H Me CF₃ Me OCH(Me)CF₃ 3081. H Me CF₃ Me OCH(Me)CH₂F 3082. H Me OCH₂CF₃ Me CF₃ 3083. H Me OCH₂CF₃ Me CHF₂ 3084. H Me CHF₂ Me CHF₂ 3085. H Me CF₃ Me CHF₂ 3086. H Me Cl Me OCHF₂ 3087. H Me Br Me OCHF₂ 3088. H Me Br Me CF₃ 3089. NO₂ H CF₃ Ph Cl 3090. NO₂ H CF₃ ^(t)Bu Cl 3091. NO₂ H CF₃ CHF₂ Cl 3092. NO₂ H Cl CHF₂ CF₃ 3093. NO₂ H CF₃ Me OMe 3094. NO₂ H CF₃ Me CN 3095. NO₂ H Cl Et Cl 3096. NO₂ H CHF₂ Me Cl 3097. NO₂ H Me Me Me 3098. NO₂ H Me Me Cl 3099. NO₂ H Cl Me Cl 3100. NO₂ H CF₃ Me Cl 3101. NO₂ H Cl Me CF₃ 3102. NO₂ H CF₃ Me F 3103. NO₂ H OMe Me CF₃ 3104. NO₂ H CF₃ Me OEt 3105. NO₂ H CF₃ Me OCHF₂ 3106. NO₂ H OCHF₂ Me CF₃ 3107. NO₂ H CF₃ Me OCH₂CHF₂ 3108. NO₂ H CF₃ Me OCH₂CF₃ 3109. NO₂ H CF₃ Me OCH₂CN 3110. NO₂ H CF₃ Me SO₂Me 3111. NO₂ H CF₃ Me SEt 3112. NO₂ H CF₃ Me Me 3113. NO₂ H CF₃ Me Et 3114. NO₂ H CF₃ Et Cl 3115. NO₂ H Cl Et CF₃ 3116. NO₂ H CF₃ ^(i)Pr Cl 3117. NO₂ H Cl ^(i)Pr CF₃ 3118. NO₂ H CF₃ ^(t)Bu Cl 3119. NO₂ H Cl ^(t)Bu CF₃ 3120. NO₂ H CF₃ cPen Cl 3121. NO₂ H Cl cPen CF₃ 3122. NO₂ H CF₃ CH₂Pr Cl 3123. NO₂ H Cl CH₂Pr CF₃ 3124. NO₂ H CF₃ CH₂CH═CH₂ Cl 3125. NO₂ H Cl CH₂CH═CH₂ CF₃ 3126. NO₂ H CF₃ CHF₂ OMe 3127. NO₂ H OMe CHF₂ CF₃ 3128. NO₂ H CF₃ CH₂CF₃ Cl 3129. NO₂ H Cl CH₂CF₃ CF₃ 3130. NO₂ H CF₃ CH₂OMe Cl 3131. NO₂ H Cl CH₂OMe CF₃ 3132. NO₂ H CF₃ CH₂CN Cl 3133. NO₂ H Me Ph Me 3134. NO₂ H Me Ph Cl 3135. NO₂ H Et Ph Cl 3136. NO₂ H Pr Ph Cl 3137. NO₂ H ^(i)Pr Ph Cl 3138. NO₂ H CF₃ Ph Cl 3139. NO₂ H CF₃ Ph Me 3140. NO₂ H CF₃ Ph CF₃ 3141. NO₂ H CF₃ Ph F 3142. NO₂ H CF₃ Ph OMe 3143. NO₂ H CF₃ Ph OEt 3144. NO₂ H CF₃ Ph OCHF₂ 3145. NO₂ H CF₃ Ph CN 3146. NO₂ H CF₃ Ph(4-Cl) Cl 3147. NO₂ H Me Me OCH₂CF₃ 3148. NO₂ H CF₃ Me

3149. NO₂ H CF₃ Me H 3150. NO₂ H CF₃ Me OCH₂CH₂OMe 3151. NO₂ H CF₃ Me SMe 3152. NO₂ H CF₃ Me OCH₂CH₂CH₂F 3153. NO₂ H CF₃ Me OCH(CH₂F)₂ 3154. NO₂ H CF₃ Me OCH₂CF₂CHF₂ 3155. NO₂ H CF₃ Me OCH₂CF═CH₂ 3156. NO₂ H CF₃ Me OCH(Me)CF₃ 3157. NO₂ H CF₃ Me OCH(Me)CH₂F 3158. NO₂ H OCH₂CF₃ Me CF₃ 3159. NO₂ H OCH₂CF₃ Me CHF₂ 3160. NO₂ H CHF₂ Me CHF₂ 3161. NO₂ H CF₃ Me CHF₂ 3162. NO₂ H Cl Me OCHF₂ 3163. NO₂ H Br Me OCHF₂ 3164. NO₂ H Br Me CF₃ 3165. CHF₂ H CF₃ Ph Cl 3166. CHF₂ H CF₃ ^(t)Bu Cl 3167. CHF₂ H CF₃ CHF₂ Cl 3168. CHF₂ H Cl CHF₂ CF₃ 3169. CHF₂ H CF₃ Me OMe 3170. CHF₂ H CF₃ Me CN 3171. CHF₂ H Cl Et Cl 3172. CHF₂ H CHF₂ Me Cl 3173. CHF₂ H Me Me Me 3174. CHF₂ H Me Me Cl 3175. CHF₂ H Cl Me Cl 3176. CHF₂ H CF₃ Me Cl 3177. CHF₂ H Cl Me CF₃ 3178. CHF₂ H CF₃ Me F 3179. CHF₂ H OMe Me CF₃ 3180. CHF₂ H CF₃ Me OEt 3181. CHF₂ H CF₃ Me OCHF₂ 3182. CHF₂ H OCHF₂ Me CF₃ 3183. CHF₂ H CF₃ Me OCH₂CHF₂ 3184. CHF₂ H CF₃ Me OCH₂CF₃ 3185. CHF₂ H CF₃ Me OCH₂CN 3186. CHF₂ H CF₃ Me SO₂Me 3187. CHF₂ H CF₃ Me SEt 3188. CHF₂ H CF₃ Me Me 3189. CHF₂ H CF₃ Me Et 3190. CHF₂ H CF₃ Et Cl 3191. CHF₂ H Cl Et CF₃ 3192. CHF₂ H CF₃ ^(i)Pr Cl 3193. CHF₂ H Cl ^(i)Pr CF₃ 3194. CHF₂ H CF₃ ^(t)Bu Cl 3195. CHF₂ H Cl ^(t)Bu CF₃ 3196. CHF₂ H CF₃ cPen Cl 3197. CHF₂ H Cl cPen CF₃ 3198. CHF₂ H CF₃ CH₂cPr Cl 3199. CHF₂ H Cl CH₂cPr CF₃ 3200. CHF₂ H CF₃ CH₂CH═CH₂ Cl 3201. CHF₂ H Cl CH₂CH═CH₂ CF₃ 3202. CHF₂ H CF₃ CHF₂ OMe 3203. CHF₂ H OMe CHF₂ CF₃ 3204. CHF₂ H CF₃ CH₂CF₃ Cl 3205. CHF₂ H Cl CH₂CF₃ CF₃ 3206. CHF₂ H CF₃ CH₂OMe Cl 3207. CHF₂ H Cl CH₂OMe CF₃ 3208. CHF₂ H CF₃ CH₂CN Cl 3209. CHF₂ H Me Ph Me 3210. CHF₂ H Me Ph Cl 3211. CHF₂ H Et Ph Cl 3212. CHF₂ H Pr Ph Cl 3213. CHF₂ H ^(i)Pr Ph Cl 3214. CHF₂ H CF₃ Ph Cl 3215. CHF₂ H CF₃ Ph Me 3216. CHF₂ H CF₃ Ph CF₃ 3217. CHF₂ H CF₃ Ph F 3218. CHF₂ H CF₃ Ph OMe 3219. CHF₂ H CF₃ Ph OEt 3220. CHF₂ H CF₃ Ph OCHF₂ 3221. CHF₂ H CF₃ Ph CN 3222. CHF₂ H CF₃ Ph(4-Cl) Cl 3223. CHF₂ H Me Me OCH₂CF₃ 3224. CHF₂ H CF₃ Me

3225. CHF₂ H CF₃ Me H 3226. CHF₂ H CF₃ Me OCH₂CH₂OMe 3227. CHF₂ H CF₃ Me SMe 3228. CHF₂ H CF₃ Me OCH₂CH₂CH₂F 3229. CHF₂ H CF₃ Me OCH(CH₂F)₂ 3230. CHF₂ H CF₃ Me OCH₂CF₂CHF₂ 3231. CHF₂ H CF₃ Me OCH₂CF═CH₂ 3232. CHF₂ H CF₃ Me OCH(Me)CF₃ 3233. CHF₂ H CF₃ Me OCH(Me)CH₂F 3234. CHF₂ H OCH₂CF₃ Me CF₃ 3235. CHF₂ H OCH₂CF₃ Me CHF₂ 3236. CHF₂ H CHF₂ Me CHF₂ 3237. CHF₂ H CF₃ Me CHF₂ 3238. CHF₂ H Cl Me OCHF₂ 3239. CHF₂ H Br Me OCHF₂ 3240. CHF₂ H Br Me CF₃ 3241. Cl Cl CF₃ Ph Cl 3242. Cl Cl CF₃ ^(t)Bu Cl 3243. Cl Cl CF₃ CHF₂ Cl 3244. Cl Cl Cl CHF₂ CF₃ 3245. Cl Cl CF₃ Me OMe 3246. Cl Cl CF₃ Me CN 3247. Cl Cl Cl Et Cl 3248. Cl Cl CHF₂ Me Cl 3249. Cl Cl Me Me Me 3250. Cl Cl Me Me Cl 3251. Cl Cl Cl Me Cl 3252. Cl Cl CF₃ Me Cl 3253. Cl Cl Cl Me CF₃ 3254. Cl Cl CF₃ Me F 3255. Cl Cl OMe Me CF₃ 3256. Cl Cl CF₃ Me OEt 3257. Cl Cl CF₃ Me OCHF₂ 3258. Cl Cl OCHF₂ Me CF₃ 3259. Cl Cl CF₃ Me OCH₂CHF₂ 3260. Cl Cl CF₃ Me OCH₂CF₃ 3261. Cl Cl CF₃ Me OCH₂CN 3262. Cl Cl CF₃ Me SO₂Me 3263. Cl Cl CF₃ Me SEt 3264. Cl Cl CF₃ Me Me 3265. Cl Cl CF₃ Me Et 3266. Cl Cl CF₃ Et Cl 3267. Cl Cl Cl Et CF₃ 3268. Cl Cl CF₃ ^(i)Pr Cl 3269. Cl Cl Cl ^(i)Pr CF₃ 3270. Cl Cl CF₃ ^(t)Bu Cl 3271. Cl Cl Cl ^(t)Bu CF₃ 3272. Cl Cl CF₃ cPen Cl 3273. Cl Cl Cl cPen CF₃ 3274. Cl Cl CF₃ CH₂cPr Cl 3275. Cl Cl Cl CH₂cPr CF₃ 3276. Cl Cl CF₃ CH₂CH═CH₂ Cl 3277. Cl Cl Cl CH₂CH═CH₂ CF₃ 3278. Cl Cl CF₃ CHF₂ OMe 3279. Cl Cl OMe CHF₂ CF₃ 3280. Cl Cl CF₃ CH₂CF₃ Cl 3281. Cl Cl Cl CH₂CF₃ CF₃ 3282. Cl Cl CF₃ CH₂OMe Cl 3283. Cl Cl Cl CH₂OMe CF₃ 3284. Cl Cl CF₃ CH₂CN Cl 3285. Cl Cl Me Ph Me 3286. Cl Cl Me Ph Cl 3287. Cl Cl Et Ph Cl 3288. Cl Cl Pr Ph Cl 3289. Cl Cl ^(i)Pr Ph Cl 3290. Cl Cl CF₃ Ph Cl 3291. Cl Cl CF₃ Ph Me 3292. Cl Cl CF₃ Ph CF₃ 3293. Cl Cl CF₃ Ph F 3294. Cl Cl CF₃ Ph OMe 3295. Cl Cl CF₃ Ph OEt 3296. Cl Cl CF₃ Ph OCHF₂ 3297. Cl Cl CF₃ Ph CN 3298. Cl Cl CF₃ Ph(4-Cl) Cl 3299. Cl Cl Me Me OCH₂CF₃ 3300. Cl Cl CF₃ Me

3301. Cl Cl CF₃ Me H 3302. Cl Cl CF₃ Me OCH₂CH₂OMe 3303. Cl Cl CF₃ Me SMe 3304. Cl Cl CF₃ Me OCH₂CH₂CH₂F 3305. Cl Cl CF₃ Me OCH(CH₂F)₂ 3306. Cl Cl CF₃ Me OCH₂CF₂CHF₂ 3307. Cl Cl CF₃ Me OCH₂CF═CH₂ 3308. Cl Cl CF₃ Me OCH(Me)CF₃ 3309. Cl Cl CF₃ Me OCH(Me)CH₂F 3310. Cl Cl OCH₂CF₃ Me CF₃ 3311. Cl Cl OCH₂CF₃ Me CHF₂ 3312. Cl Cl CHF₂ Me CHF₂ 3313. Cl Cl CF₃ Me CHF₂ 3314. Cl Cl Cl Me OCHF₂ 3315. Cl Cl Br Me OCHF₂ 3316. Cl Cl Br Me CF₃ 3317. Me Cl CF₃ Ph Cl 3318. Me Cl CF₃ ^(t)Bu Cl 3319. Me Cl CF₃ CHF₂ Cl 3320. Me Cl Cl CHF₂ CF₃ 3321. Me Cl CF₃ Me OMe 3322. Me Cl CF₃ Me CN 3323. Me Cl Cl Et Cl 3324. Me Cl CHF₂ Me Cl 3325. Me Cl Me Me Me 3326. Me Cl Me Me Cl 3327. Me Cl Cl Me Cl 3328. Me Cl CF₃ Me Cl 3329. Me Cl Cl Me CF₃ 3330. Me Cl CF₃ Me F 3331. Me Cl OMe Me CF₃ 3332. Me Cl CF₃ Me OEt 3333. Me Cl CF₃ Me OCHF₂ 3334. Me Cl OCHF₂ Me CF₃ 3335. Me Cl CF₃ Me OCH₂CHF₂ 3336. Me Cl CF₃ Me OCH₂CF₃ 3337. Me Cl CF₃ Me OCH₂CN 3338. Me Cl CF₃ Me SO₂Me 3339. Me Cl CF₃ Me SEt 3340. Me Cl CF₃ Me Me 3341. Me Cl CF₃ Me Et 3342. Me Cl CF₃ Et Cl 3343. Me Cl Cl Et CF₃ 3344. Me Cl CF₃ ^(i)Pr Cl 3345. Me Cl Cl ^(i)Pr CF₃ 3346. Me Cl CF₃ ^(t)Bu Cl 3347. Me Cl Cl ^(t)Bu CF₃ 3348. Me Cl CF₃ cPen Cl 3349. Me Cl Cl cPen CF₃ 3350. Me Cl CF₃ CH₂cPr Cl 3351. Me Cl Cl CH₂cPr CF₃ 3352. Me Cl CF₃ CH₂CH═CH₂ Cl 3353. Me Cl Cl CH₂CH═CH₂ CF₃ 3354. Me Cl CF₃ CHF₂ OMe 3355. Me Cl OMe CHF₂ CF₃ 3356. Me Cl CF₃ CH₂CF₃ Cl 3357. Me Cl Cl CH₂CF₃ CF₃ 3358. Me Cl CF₃ CH₂OMe Cl 3359. Me Cl Cl CH₂OMe CF₃ 3360. Me Cl CF₃ CH₂CN Cl 3361. Me Cl Me Ph Me 3362. Me Cl Me Ph Cl 3363. Me Cl Et Ph Cl 3364. Me Cl Pr Ph Cl 3365. Me Cl ^(i)Pr Ph Cl 3366. Me Cl CF₃ Ph Cl 3367. Me Cl CF₃ Ph Me 3368. Me Cl CF₃ Ph CF₃ 3369. Me Cl CF₃ Ph F 3370. Me Cl CF₃ Ph OMe 3371. Me Cl CF₃ Ph OEt 3372. Me Cl CF₃ Ph OCHF₂ 3373. Me Cl CF₃ Ph CN 3374. Me Cl CF₃ Ph(4-Cl) Cl 3375. Me Cl Me Me OCH₂CF₃ 3376. Me Cl CF₃ Me

3377. Me Cl CF₃ Me H 3378. Me Cl CF₃ Me OCH₂CH₂OMe 3379. Me Cl CF₃ Me SMe 3380. Me Cl CF₃ Me OCH₂CH₂CH₂F 3381. Me Cl CF₃ Me OCH(CH₂F)₂ 3382. Me Cl CF₃ Me OCH₂CF₂CHF₂ 3383. Me Cl CF₃ Me OCH₂CF═CH₂ 3384. Me Cl CF₃ Me OCH(Me)CF₃ 3385. Me Cl CF₃ Me OCH(Me)CH₂F 3386. Me Cl OCH₂CF₃ Me CF₃ 3387. Me Cl OCH₂CF₃ Me CHF₂ 3388. Me Cl CHF₂ Me CHF₂ 3389. Me Cl CF₃ Me CHF₂ 3390. Me Cl Cl Me OCHF₂ 3391. Me Cl Br Me OCHF₂ 3392. Me Cl Br Me CF₃ 3393. Cl Me CF₃ Ph Cl 3394. Cl Me CF₃ ^(t)Bu Cl 3395. Cl Me CF₃ CHF₂ Cl 3396. Cl Me Cl CHF₂ CF₃ 3397. Cl Me CF₃ Me OMe 3398. Cl Me CF₃ Me CN 3399. Cl Me Cl Et Cl 3400. Cl Me CHF₂ Me Cl 3401. Cl Me Me Me Me 3402. Cl Me Me Me Cl 3403. Cl Me Cl Me Cl 3404. Cl Me CF₃ Me Cl 3405. Cl Me Cl Me CF₃ 3406. Cl Me CF₃ Me F 3407. Cl Me OMe Me CF₃ 3408. Cl Me CF₃ Me OEt 3409. Cl Me CF₃ Me OCHF₂ 3410. Cl Me OCHF₂ Me CF₃ 3411. Cl Me CF₃ Me OCH₂CHF₂ 3412. Cl Me CF₃ Me OCH₂CF₃ 3413. Cl Me CF₃ Me OCH₂CN 3414. Cl Me CF₃ Me SO₂Me 3415. Cl Me CF₃ Me SEt 3416. Cl Me CF₃ Me Me 3417. Cl Me CF₃ Me Et 3418. Cl Me CF₃ Et Cl 3419. Cl Me Cl Et CF₃ 3420. Cl Me CF₃ ^(i)Pr Cl 3421. Cl Me Cl ^(i)Pr CF₃ 3422. Cl Me CF₃ ^(t)Bu Cl 3423. Cl Me Cl ^(t)Bu CF₃ 3424. Cl Me CF₃ cPen Cl 3425. Cl Me Cl cPen CF₃ 3426. Cl Me CF₃ CH₂cPr Cl 3427. Cl Me Cl CH₂cPr CF₃ 3428. Cl Me CF₃ CH₂CH═CH₂ Cl 3429. Cl Me Cl CH₂CH═CH₂ CF₃ 3430. Cl Me CF₃ CHF₂ OMe 3431. Cl Me OMe CHF₂ CF₃ 3432. Cl Me CF₃ CH₂CF₃ Cl 3433. Cl Me Cl CH₂CF₃ CF₃ 3434. Cl Me CF₃ CH₂OMe Cl 3435. Cl Me Cl CH₂OMe CF₃ 3436. Cl Me CF₃ CH₂CN Cl 3437. Cl Me Me Ph Me 3438. Cl Me Me Ph Cl 3439. Cl Me Et Ph Cl 3440. Cl Me Pr Ph Cl 3441. Cl Me ^(i)Pr Ph Cl 3442. Cl Me CF₃ Ph Cl 3443. Cl Me CF₃ Ph Me 3444. Cl Me CF₃ Ph CF₃ 3445. Cl Me CF₃ Ph F 3446. Cl Me CF₃ Ph OMe 3447. Cl Me CF₃ Ph OEt 3448. Cl Me CF₃ Ph OCHF₂ 3449. Cl Me CF₃ Ph CN 3450. Cl Me CF₃ Ph(4-Cl) Cl 3451. Cl Me Me Me OCH₂CF₃ 3452. Cl Me CF₃ Me

3453. Cl Me CF₃ Me H 3454. Cl Me CF₃ Me OCH₂CH₂OMe 3455. Cl Me CF₃ Me SMe 3456. Cl Me CF₃ Me OCH₂CH₂CH₂F 3457. Cl Me CF₃ Me OCH(CH₂F)₂ 3458. Cl Me CF₃ Me OCH₂CF₂CHF₂ 3459. Cl Me CF₃ Me OCH₂CF═CH₂ 3460. Cl Me CF₃ Me OCH(Me)CF₃ 3461. Cl Me CF₃ Me OCH(Me)CH₂F 3462. Cl Me OCH₂CF₃ Me CF₃ 3463. Cl Me OCH₂CF₃ Me CHF₂ 3464. Cl Me CHF₂ Me CHF₂ 3465. Cl Me CF₃ Me CHF₂ 3466. Cl Me Cl Me OCHF₂ 3467. Cl Me Br Me OCHF₂ 3468. Cl Me Br Me CF₃

TABLE 4 Compounds of the formula Ib-R (Ib-R)

Ex. No. R¹¹ R¹² R⁶ R⁷ R⁸ 3469. H H CF₃ Ph Cl 3470. H H CF₃ ^(t)Bu Cl 3471. H H CF₃ CHF₂ Cl 3472. H H Cl CHF₂ CF₃ 3473. H H CF₃ Me OMe 3474. H H CF₃ Me CN 3475. H H Cl Et Cl 3476. H H CHF₂ Me Cl 3477. H H Me Me Me 3478. H H Me Me Cl 3479. H H Cl Me Cl 3480. H H CF₃ Me Cl 3481. H H Cl Me CF₃ 3482. H H CF₃ Me F 3483. H H OMe Me CF₃ 3484. H H CF₃ Me OEt 3485. H H CF₃ Me OCHF₂ 3486. H H OCHF₂ Me CF₃ 3487. H H CF₃ Me OCH₂CHF₂ 3488. H H CF₃ Me OCH₂CF₃ 3489. H H CF₃ Me OCH₂CN 3490. H H CF₃ Me SO₂Me 3491. H H CF₃ Me SEt 3492. H H CF₃ Me Me 3493. H H CF₃ Me Et 3494. H H CF₃ Et Cl 3495. H H Cl Et CF₃ 3496. H H CF₃ ^(i)Pr Cl 3497. H H Cl ^(i)Pr CF₃ 3498. H H CF₃ ^(t)Bu Cl 3499. H H Cl ^(t)Bu CF₃ 3500. H H CF₃ cPen Cl 3501. H H Cl cPen CF₃ 3502. H H CF₃ CH₂cPr Cl 3503. H H Cl CH₂cPr CF₃ 3504. H H CF₃ CH₂CH═CH₂ Cl 3505. H H Cl CH₂CH═CH₂ CF₃ 3506. H H CF₃ CHF₂ OMe 3507. H H OMe CHF₂ CF₃ 3508. H H CF₃ CH₂CF₃ Cl 3509. H H Cl CH₂CF₃ CF₃ 3510. H H CF₃ CH₂OMe Cl 3511. H H Cl CH₂OMe CF₃ 3512. H H CF₃ CH₂CN Cl 3513. H H Me Ph Me 3514. H H Me Ph Cl 3515. H H Et Ph Cl 3516. H H Pr Ph Cl 3517. H H ^(i)Pr Ph Cl 3518. H H CF₃ Ph Cl 3519. H H CF₃ Ph Me 3520. H H CF₃ Ph CF₃ 3521. H H CF₃ Ph F 3522. H H CF₃ Ph OMe 3523. H H CF₃ Ph OEt 3524. H H CF₃ Ph OCHF₂ 3525. H H CF₃ Ph CN 3526. H H CF₃ Ph(4-Cl) Cl 3527. H H Me Me OCH₂CF₃ 3528. H H CF₃ Me

3529. H H CF₃ Me H 3530. H H CF₃ Me OCH₂CH₂OMe 3531. H H CF₃ Me SMe 3532. H H CF₃ Me OCH₂CH₂CH₂F 3533. H H CF₃ Me OCH(CH₂F)₂ 3534. H H CF₃ Me OCH₂CF₂CHF₂ 3535. H H CF₃ Me OCH₂CF═CH₂ 3536. H H CF₃ Me OCH(Me)CF₃ 3537. H H CF₃ Me OCH(Me)CH₂F 3538. H H OCH₂CF₃ Me CF₃ 3539. H H OCH₂CF₃ Me CHF₂ 3540. H H CHF₂ Me CHF₂ 3541. H H CF₃ Me CHF₂ 3542. H H Cl Me OCHF₂ 3543. H H Br Me OCHF₂ 3544. H H Br Me CF₃ 3545. F H CF₃ Ph Cl 3546. F H CF₃ ^(t)Bu Cl 3547. F H CF₃ CHF₂ Cl 3548. F H Cl CHF₂ CF₃ 3549. F H CF₃ Me OMe 3550. F H CF₃ Me CN 3551. F H Cl Et Cl 3552. F H CHF₂ Me Cl 3553. F H Me Me Me 3554. F H Me Me Cl 3555. F H Cl Me Cl 3556. F H CF₃ Me Cl 3557. F H Cl Me CF₃ 3558. F H CF₃ Me F 3559. F H OMe Me CF₃ 3560. F H CF₃ Me OEt 3561. F H CF₃ Me OCHF₂ 3562. F H OCHF₂ Me CF₃ 3563. F H CF₃ Me OCH₂CHF₂ 3564. F H CF₃ Me OCH₂CF₃ 3565. F H CF₃ Me OCH₂CN 3566. F H CF₃ Me SO₂Me 3567. F H CF₃ Me SEt 3568. F H CF₃ Me Me 3569. F H CF₃ Me Et 3570. F H CF₃ Et Cl 3571. F H Cl Et CF₃ 3572. F H CF₃ ^(i)Pr Cl 3573. F H Cl ^(i)Pr CF₃ 3574. F H CF₃ ^(t)Bu Cl 3575. F H Cl ^(t)Bu CF₃ 3576. F H CF₃ cPen Cl 3577. F H Cl cPen CF₃ 3578. F H CF₃ CH₂cPr Cl 3579. F H Cl CH₂cPr CF₃ 3580. F H CF₃ CH₂CH═CH₂ Cl 3581. F H Cl CH₂CH═CH₂ CF₃ 3582. F H CF₃ CHF₂ OMe 3583. F H OMe CHF₂ CF₃ 3584. F H CF₃ CH₂CF₃ Cl 3585. F H Cl CH₂CF₃ CF₃ 3586. F H CF₃ CH₂OMe Cl 3587. F H Cl CH₂OMe CF₃ 3588. F H CF₃ CH₂CN Cl 3589. F H Me Ph Me 3590. F H Me Ph Cl 3591. F H Et Ph Cl 3592. F H Pr Ph Cl 3593. F H ^(i)Pr Ph Cl 3594. F H CF₃ Ph Cl 3595. F H CF₃ Ph Me 3596. F H CF₃ Ph CF₃ 3597. F H CF₃ Ph F 3598. F H CF₃ Ph OMe 3599. F H CF₃ Ph OEt 3600. F H CF₃ Ph OCHF₂ 3601. F H CF₃ Ph CN 3602. F H CF₃ Ph(4-Cl) Cl 3603. F H Me Me OCH₂CF₃ 3604. F H CF₃ Me

3605. F H CF₃ Me H 3606. F H CF₃ Me OCH₂CH₂OMe 3607. F H CF₃ Me SMe 3608. F H CF₃ Me OCH₂CH₂CH₂F 3609. F H CF₃ Me OCH(CH₂F)₂ 3610. F H CF₃ Me OCH₂CF₂CHF₂ 3611. F H CF₃ Me OCH₂CF═CH₂ 3612. F H CF₃ Me OCH(Me)CF₃ 3613. F H CF₃ Me OCH(Me)CH₂F 3614. F H OCH₂CF₃ Me CF₃ 3615. F H OCH₂CF₃ Me CHF₂ 3616. F H CHF₂ Me CHF₂ 3617. F H CF₃ Me CHF₂ 3618. F H Cl Me OCHF₂ 3619. F H Br Me OCHF₂ 3620. F H Br Me CF₃ 3621. F H CF₃ Me CF₃ 3622. F H CHF₂ Me OCHF₂ 3623. F H CHF₂ Me CF₃ 3624. F H CF₂CF₃ Me CF₃ 3625. F H CF₃ Me CF₂CF₃ 3626. F H CHF₂ Me OCH₂CF₃ 3627. Cl H CF₃ Ph Cl 3628. Cl H CF₃ ^(t)Bu Cl 3629. Cl H CF₃ CHF₂ Cl 3630. Cl H Cl CHF₂ CF₃ 3631. Cl H CF₃ Me OMe 3632. Cl H CF₃ Me CN 3633. Cl H Cl Et Cl 3634. Cl H CHF₂ Me Cl 3635. Cl H Me Me Me 3636. Cl H Me Me Cl 3637. Cl H Cl Me Cl 3638. Cl H CF₃ Me Cl 3639. Cl H Cl Me CF₃ 3640. Cl H CF₃ Me F 3641. Cl H OMe Me CF₃ 3642. Cl H CF₃ Me OEt 3643. Cl H CF₃ Me OCHF₂ 3644. Cl H OCHF₂ Me CF₃ 3645. Cl H CF₃ Me OCH₂CHF₂ 3646. Cl H CF₃ Me OCH₂CF₃ 3647. Cl H CF₃ Me OCH₂CN 3648. Cl H CF₃ Me SO₂Me 3649. Cl H CF₃ Me SEt 3650. Cl H CF₃ Me Me 3651. Cl H CF₃ Me Et 3652. Cl H CF₃ Et Cl 3653. Cl H Cl Et CF₃ 3654. Cl H CF₃ ^(i)Pr Cl 3655. Cl H Cl ^(i)Pr CF₃ 3656. Cl H CF₃ ^(t)Bu Cl 3657. Cl H Cl ^(t)Bu CF₃ 3658. Cl H CF₃ cPen Cl 3659. Cl H Cl cPen CF₃ 3660. Cl H CF₃ CH₂cPr Cl 3661. Cl H Cl CH₂cPr CF₃ 3662. Cl H CF₃ CH₂CH═CH₂ Cl 3663. Cl H Cl CH₂CH═CH₂ CF₃ 3664. Cl H CF₃ CHF₂ OMe 3665. Cl H OMe CHF₂ CF₃ 3666. Cl H CF₃ CH₂CF₃ Cl 3667. Cl H Cl CH₂CF₃ CF₃ 3668. Cl H CF₃ CH₂OMe Cl 3669. Cl H Cl CH₂OMe CF₃ 3670. Cl H CF₃ CH₂CN Cl 3671. Cl H Me Ph Me 3672. Cl H Me Ph Cl 3673. Cl H Et Ph Cl 3674. Cl H Pr Ph Cl 3675. Cl H ^(i)Pr Ph Cl 3676. Cl H CF₃ Ph Cl 3677. Cl H CF₃ Ph Me 3678. Cl H CF₃ Ph CF₃ 3679. Cl H CF₃ Ph F 3680. Cl H CF₃ Ph OMe 3681. Cl H CF₃ Ph OEt 3682. Cl H CF₃ Ph OCHF₂ 3683. Cl H CF₃ Ph CN 3684. Cl H CF₃ Ph(4-Cl) Cl 3685. Cl H Me Me OCH₂CF₃ 3686. Cl H CF₃ Me

3687. Cl H CF₃ Me H 3688. Cl H CF₃ Me OCH₂CH₂OMe 3689. Cl H CF₃ Me SMe 3690. Cl H CF₃ Me OCH₂CH₂CH₂F 3691. Cl H CF₃ Me OCH(CH₂F)₂ 3692. Cl H CF₃ Me OCH₂CF₂CHF₂ 3693. Cl H CF₃ Me OCH₂CF═CH₂ 3694. Cl H CF₃ Me OCH(Me)CF₃ 3695. Cl H CF₃ Me OCH(Me)CH₂F 3696. Cl H OCH₂CF₃ Me CF₃ 3697. Cl H OCH₂CF₃ Me CHF₂ 3698. Cl H CHF₂ Me CHF₂ 3699. Cl H CF₃ Me CHF₂ 3700. Cl H Cl Me OCHF₂ 3701. Cl H Br Me OCHF₂ 3702. Cl H Br Me CF₃ 3703. Cl H CF₃ Me CF₃ 3704. Cl H CHF₂ Me OCHF₂ 3705. Cl H CHF₂ Me CF₃ 3706. Cl H CF₂CF₃ Me CF₃ 3707. Cl H CF₃ Me CF₂CF₃ 3708. Cl H CHF₂ Me OCH₂CF₃ 3709. Br H CF₃ Ph Cl 3710. Br H CF₃ ^(t)Bu Cl 3711. Br H CF₃ CHF₂ Cl 3712. Br H Cl CHF₂ CF₃ 3713. Br H CF₃ Me OMe 3714. Br H CF₃ Me CN 3715. Br H Cl Et Cl 3716. Br H CHF₂ Me Cl 3717. Br H Me Me Me 3718. Br H Me Me Cl 3719. Br H Cl Me Cl 3720. Br H CF₃ Me Cl 3721. Br H Cl Me CF₃ 3722. Br H CF₃ Me F 3723. Br H OMe Me CF₃ 3724. Br H CF₃ Me OEt 3725. Br H CF₃ Me OCHF₂ 3726. Br H OCHF₂ Me CF₃ 3727. Br H CF₃ Me OCH₂CHF₂ 3728. Br H CF₃ Me OCH₂CF₃ 3729. Br H CF₃ Me OCH₂CN 3730. Br H CF₃ Me SO₂Me 3731. Br H CF₃ Me SEt 3732. Br H CF₃ Me Me 3733. Br H CF₃ Me Et 3734. Br H CF₃ Et Cl 3735. Br H Cl Et CF₃ 3736. Br H CF₃ ^(i)Pr Cl 3737. Br H Cl ^(i)Pr CF₃ 3738. Br H CF₃ ^(t)Bu Cl 3739. Br H Cl ^(t)Bu CF₃ 3740. Br H CF₃ cPen Cl 3741. Br H Cl cPen CF₃ 3742. Br H CF₃ CH₂cPr Cl 3743. Br H Cl CH₂cPr CF₃ 3744. Br H CF₃ CH₂CH═CH₂ Cl 3745. Br H Cl CH₂CH═CH₂ CF₃ 3746. Br H CF₃ CHF₂ OMe 3747. Br H OMe CHF₂ CF₃ 3748. Br H CF₃ CH₂CF₃ Cl 3749. Br H Cl CH₂CF₃ CF₃ 3750. Br H CF₃ CH₂OMe Cl 3751. Br H Cl CH₂OMe CF₃ 3752. Br H CF₃ CH₂CN Cl 3753. Br H Me Ph Me 3754. Br H Me Ph Cl 3755. Br H Et Ph Cl 3756. Br H Pr Ph Cl 3757. Br H ^(i)Pr Ph Cl 3758. Br H CF₃ Ph Cl 3759. Br H CF₃ Ph Me 3760. Br H CF₃ Ph CF₃ 3761. Br H CF₃ Ph F 3762. Br H CF₃ Ph OMe 3763. Br H CF₃ Ph OEt 3764. Br H CF₃ Ph OCHF₂ 3765. Br H CF₃ Ph CN 3766. Br H CF₃ Ph(4-Cl) Cl 3767. Br H Me Me OCH₂CF₃ 3768. Br H CF₃ Me

3769. Br H CF₃ Me H 3770. Br H CF₃ Me OCH₂CH₂OMe 3771. Br H CF₃ Me SMe 3772. Br H CF₃ Me OCH₂CH₂CH₂F 3773. Br H CF₃ Me OCH(CH₂F)₂ 3774. Br H CF₃ Me OCH₂CF₂CHF₂ 3775. Br H CF₃ Me OCH₂CF═CH₂ 3776. Br H CF₃ Me OCH(Me)CF₃ 3777. Br H CF₃ Me OCH(Me)CH₂F 3778. Br H OCH₂CF₃ Me CF₃ 3779. Br H OCH₂CF₃ Me CHF₂ 3780. Br H CHF₂ Me CHF₂ 3781. Br H CF₃ Me CHF₂ 3782. Br H Cl Me OCHF₂ 3783. Br H Br Me OCHF₂ 3784. Br H Br Me CF₃ 3785. Br H CF₃ Me CF₃ 3786. Br H CHF₂ Me OCHF₂ 3787. Br H CHF₂ Me CF₃ 3788. Br H CF₂CF₃ Me CF₃ 3789. Br H CF₃ Me CF₂CF₃ 3790. Br H CHF₂ Me OCH₂CF₃ 3791. I H CF₃ Ph Cl 3792. I H CF₃ ^(t)Bu Cl 3793. I H CF₃ CHF₂ Cl 3794. I H Cl CHF₂ CF₃ 3795. I H CF₃ Me OMe 3796. I H CF₃ Me CN 3797. I H Cl Et Cl 3798. I H CHF₂ Me Cl 3799. I H Me Me Me 3800. I H Me Me Cl 3801. I H Cl Me Cl 3802. I H CF₃ Me Cl 3803. I H Cl Me CF₃ 3804. I H CF₃ Me F 3805. I H OMe Me CF₃ 3806. I H CF₃ Me OEt 3807. I H CF₃ Me OCHF₂ 3808. I H OCHF₂ Me CF₃ 3809. I H CF₃ Me OCH₂CHF₂ 3810. I H CF₃ Me OCH₂CF₃ 3811. I H CF₃ Me OCH₂CN 3812. I H CF₃ Me SO₂Me 3813. I H CF₃ Me SEt 3814. I H CF₃ Me Me 3815. I H CF₃ Me Et 3816. I H CF₃ Et Cl 3817. I H Cl Et CF₃ 3818. I H CF₃ ^(i)Pr Cl 3819. I H Cl ^(i)Pr CF₃ 3820. I H CF₃ ^(t)Bu Cl 3821. I H Cl ^(t)Bu CF₃ 3822. I H CF₃ cPen Cl 3823. I H Cl cPen CF₃ 3824. I H CF₃ CH₂cPr Cl 3825. I H Cl CH₂cPr CF₃ 3826. I H CF₃ CH₂CH═CH₂ Cl 3827. I H Cl CH₂CH═CH₂ CF₃ 3828. I H CF₃ CHF₂ OMe 3829. I H OMe CHF₂ CF₃ 3830. I H CF₃ CH₂CF₃ Cl 3831. I H Cl CH₂CF₃ CF₃ 3832. I H CF₃ CH₂OMe Cl 3833. I H Cl CH₂OMe CF₃ 3834. I H CF₃ CH₂CN Cl 3835. I H Me Ph Me 3836. I H Me Ph Cl 3837. I H Et Ph Cl 3838. I H Pr Ph Cl 3839. I H ^(i)Pr Ph Cl 3840. I H CF₃ Ph Cl 3841. I H CF₃ Ph Me 3842. I H CF₃ Ph CF₃ 3843. I H CF₃ Ph F 3844. I H CF₃ Ph OMe 3845. I H CF₃ Ph OEt 3846. I H CF₃ Ph OCHF₂ 3847. I H CF₃ Ph CN 3848. I H CF₃ Ph(4-Cl) Cl 3849. I H Me Me OCH₂CF₃ 3850. I H CF₃ Me

3851. I H CF₃ Me H 3852. I H CF₃ Me OCH₂CH₂OMe 3853. I H CF₃ Me SMe 3854. I H CF₃ Me OCH₂CH₂CH₂F 3855. I H CF₃ Me OCH(CH₂F)₂ 3856. I H CF₃ Me OCH₂CF₂CHF₂ 3857. I H CF₃ Me OCH₂CF═CH₂ 3858. I H CF₃ Me OCH(Me)CF₃ 3859. I H CF₃ Me OCH(Me)CH₂F 3860. I H OCH₂CF₃ Me CF₃ 3861. I H OCH₂CF₃ Me CHF₂ 3862. I H CHF₂ Me CHF₂ 3863. I H CF₃ Me CHF₂ 3864. I H Cl Me OCHF₂ 3865. I H Br Me OCHF₂ 3866. I H Br Me CF₃ 3867. I H CF₃ Me CF₃ 3868. I H CHF₂ Me OCHF₂ 3869. I H CHF₂ Me CF₃ 3870. I H CF₂CF₃ Me CF₃ 3871. I H CF₃ Me CF₂CF₃ 3872. I H CHF₂ Me OCH₂CF₃ 3873. H Cl CF₃ Ph Cl 3874. H Cl CF₃ ^(t)Bu Cl 3875. H Cl CF₃ CHF₂ Cl 3876. H Cl Cl CHF₂ CF₃ 3877. H Cl CF₃ Me OMe 3878. H Cl CF₃ Me CN 3879. H Cl Cl Et Cl 3880. H Cl CHF₂ Me Cl 3881. H Cl Me Me Me 3882. H Cl Me Me Cl 3883. H Cl Cl Me Cl 3884. H Cl CF₃ Me Cl 3885. H Cl Cl Me CF₃ 3886. H Cl CF₃ Me F 3887. H Cl OMe Me CF₃ 3888. H Cl CF₃ Me OEt 3889. H Cl CF₃ Me OCHF₂ 3890. H Cl OCHF₂ Me CF₃ 3891. H Cl CF₃ Me OCH₂CHF₂ 3892. H Cl CF₃ Me OCH₂CF₃ 3893. H Cl CF₃ Me OCH₂CN 3894. H Cl CF₃ Me SO₂Me 3895. H Cl CF₃ Me SEt 3896. H Cl CF₃ Me Me 3897. H Cl CF₃ Me Et 3898. H Cl CF₃ Et Cl 3899. H Cl Cl Et CF₃ 3900. H Cl CF₃ ^(i)Pr Cl 3901. H Cl Cl ^(i)Pr CF₃ 3902. H Cl CF₃ ^(t)Bu Cl 3903. H Cl Cl ^(t)Bu CF₃ 3904. H Cl CF₃ cPen Cl 3905. H Cl Cl cPen CF₃ 3906. H Cl CF₃ CH₂cPr Cl 3907. H Cl Cl CH₂cPr CF₃ 3908. H Cl CF₃ CH₂CH═CH₂ Cl 3909. H Cl Cl CH₂CH═CH₂ CF₃ 3910. H Cl CF₃ CHF₂ OMe 3911. H Cl OMe CHF₂ CF₃ 3912. H Cl CF₃ CH₂CF₃ Cl 3913. H Cl Cl CH₂CF₃ CF₃ 3914. H Cl CF₃ CH₂OMe Cl 3915. H Cl Cl CH₂OMe CF₃ 3916. H Cl CF₃ CH₂CN Cl 3917. H Cl Me Ph Me 3918. H Cl Me Ph Cl 3919. H Cl Et Ph Cl 3920. H Cl Pr Ph Cl 3921. H Cl ^(i)Pr Ph Cl 3922. H Cl CF₃ Ph Cl 3923. H Cl CF₃ Ph Me 3924. H Cl CF₃ Ph CF₃ 3925. H Cl CF₃ Ph F 3926. H Cl CF₃ Ph OMe 3927. H Cl CF₃ Ph OEt 3928. H Cl CF₃ Ph OCHF₂ 3929. H Cl CF₃ Ph CN 3930. H Cl CF₃ Ph(4-Cl) Cl 3931. H Cl Me Me OCH₂CF₃ 3932. H Cl CF₃ Me

3933. H Cl CF₃ Me H 3934. H Cl CF₃ Me OCH₂CH₂OMe 3935. H Cl CF₃ Me SMe 3936. H Cl CF₃ Me OCH₂CH₂CH₂F 3937. H Cl CF₃ Me OCH(CH₂F)₂ 3938. H Cl CF₃ Me OCH₂CF₂CHF₂ 3939. H Cl CF₃ Me OCH₂CF═CH₂ 3940. H Cl CF₃ Me OCH(Me)CF₃ 3941. H Cl CF₃ Me OCH(Me)CH₂F 3942. H Cl OCH₂CF₃ Me CF₃ 3943. H Cl OCH₂CF₃ Me CHF₂ 3944. H Cl CHF₂ Me CHF₂ 3945. H Cl CF₃ Me CHF₂ 3946. H Cl Cl Me OCHF₂ 3947. H Cl Br Me OCHF₂ 3948. H Cl Br Me CF₃ 3949. H Br CF₃ Ph Cl 3950. H Br CF₃ ^(t)Bu Cl 3951. H Br CF₃ CHF₂ Cl 3952. H Br Cl CHF₂ CF₃ 3953. H Br CF₃ Me OMe 3954. H Br CF₃ Me CN 3955. H Br Cl Et Cl 3956. H Br CHF₂ Me Cl 3957. H Br Me Me Me 3958. H Br Me Me Cl 3959. H Br Cl Me Cl 3960. H Br CF₃ Me Cl 3961. H Br Cl Me CF₃ 3962. H Br CF₃ Me F 3963. H Br OMe Me CF₃ 3964. H Br CF₃ Me OEt 3965. H Br CF₃ Me OCHF₂ 3966. H Br OCHF₂ Me CF₃ 3967. H Br CF₃ Me OCH₂CHF₂ 3968. H Br CF₃ Me OCH₂CF₃ 3969. H Br CF₃ Me OCH₂CN 3970. H Br CF₃ Me SO₂Me 3971. H Br CF₃ Me SEt 3972. H Br CF₃ Me Me 3973. H Br CF₃ Me Et 3974. H Br CF₃ Et Cl 3975. H Br Cl Et CF₃ 3976. H Br CF₃ ^(i)Pr Cl 3977. H Br Cl ^(i)Pr CF₃ 3978. H Br CF₃ ^(t)Bu Cl 3979. H Br Cl ^(t)Bu CF₃ 3980. H Br CF₃ cPen Cl 3981. H Br Cl cPen CF₃ 3982. H Br CF₃ CH₂cPr Cl 3983. H Br Cl CH₂cPr CF₃ 3984. H Br CF₃ CH₂CH═CH₂ Cl 3985. H Br Cl CH₂CH═CH₂ CF₃ 3986. H Br CF₃ CHF₂ OMe 3987. H Br OMe CHF₂ CF₃ 3988. H Br CF₃ CH₂CF₃ Cl 3989. H Br Cl CH₂CF₃ CF₃ 3990. H Br CF₃ CH₂OMe Cl 3991. H Br Cl CH₂OMe CF₃ 3992. H Br CF₃ CH₂CN Cl 3993. H Br Me Ph Me 3994. H Br Me Ph Cl 3995. H Br Et Ph Cl 3996. H Br Pr Ph Cl 3997. H Br ^(i)Pr Ph Cl 3998. H Br CF₃ Ph Cl 3999. H Br CF₃ Ph Me 4000. H Br CF₃ Ph CF₃ 4001. H Br CF₃ Ph F 4002. H Br CF₃ Ph OMe 4003. H Br CF₃ Ph OEt 4004. H Br CF₃ Ph OCHF₂ 4005. H Br CF₃ Ph CN 4006. H Br CF₃ Ph(4-Cl) Cl 4007. H Br Me Me OCH₂CF₃ 4008. H Br CF₃ Me

4009. H Br CF₃ Me H 4010. H Br CF₃ Me OCH₂CH₂OMe 4011. H Br CF₃ Me SMe 4012. H Br CF₃ Me OCH₂CH₂CH₂F 4013. H Br CF₃ Me OCH(CH₂F)₂ 4014. H Br CF₃ Me OCH₂CF₂CHF₂ 4015. H Br CF₃ Me OCH₂CF═CH₂ 4016. H Br CF₃ Me OCH(Me)CF₃ 4017. H Br CF₃ Me OCH(Me)CH₂F 4018. H Br OCH₂CF₃ Me CF₃ 4019. H Br OCH₂CF₃ Me CHF₂ 4020. H Br CHF₂ Me CHF₂ 4021. H Br CF₃ Me CHF₂ 4022. H Br Cl Me OCHF₂ 4023. H Br Br Me OCHF₂ 4024. H Br Br Me CF₃ 4025. Me H CF₃ Ph Cl 4026. Me H CF₃ ^(t)Bu Cl 4027. Me H CF₃ CHF₂ Cl 4028. Me H Cl CHF₂ CF₃ 4029. Me H CF₃ Me OMe 4030. Me H CF₃ Me CN 4031. Me H Cl Et Cl 4032. Me H CHF₂ Me Cl 4033. Me H Me Me Me 4034. Me H Me Me Cl 4035. Me H Cl Me Cl 4036. Me H CF₃ Me Cl 4037. Me H Cl Me CF₃ 4038. Me H CF₃ Me F 4039. Me H OMe Me CF₃ 4040. Me H CF₃ Me OEt 4041. Me H CF₃ Me OCHF₂ 4042. Me H OCHF₂ Me CF₃ 4043. Me H CF₃ Me OCH₂CHF₂ 4044. Me H CF₃ Me OCH₂CF₃ 4045. Me H CF₃ Me OCH₂CN 4046. Me H CF₃ Me SO₂Me 4047. Me H CF₃ Me SEt 4048. Me H CF₃ Me Me 4049. Me H CF₃ Me Et 4050. Me H CF₃ Et Cl 4051. Me H Cl Et CF₃ 4052. Me H CF₃ ^(i)Pr Cl 4053. Me H Cl ^(i)Pr CF₃ 4054. Me H CF₃ ^(t)Bu Cl 4055. Me H Cl ^(t)Bu CF₃ 4056. Me H CF₃ cPen Cl 4057. Me H Cl cPen CF₃ 4058. Me H CF₃ CH₂cPr Cl 4059. Me H Cl CH₂cPr CF₃ 4060. Me H CF₃ CH₂CH═CH₂ Cl 4061. Me H Cl CH₂CH═CH₂ CF₃ 4062. Me H CF₃ CHF₂ OMe 4063. Me H OMe CHF₂ CF₃ 4064. Me H CF₃ CH₂CF₃ Cl 4065. Me H Cl CH₂CF₃ CF₃ 4066. Me H CF₃ CH₂OMe Cl 4067. Me H Cl CH₂OMe CF₃ 4068. Me H CF₃ CH₂CN Cl 4069. Me H Me Ph Me 4070. Me H Me Ph Cl 4071. Me H Et Ph Cl 4072. Me H Pr Ph Cl 4073. Me H ^(i)Pr Ph Cl 4074. Me H CF₃ Ph Cl 4075. Me H CF₃ Ph Me 4076. Me H CF₃ Ph CF₃ 4077. Me H CF₃ Ph F 4078. Me H CF₃ Ph OMe 4079. Me H CF₃ Ph OEt 4080. Me H CF₃ Ph OCHF₂ 4081. Me H CF₃ Ph CN 4082. Me H CF₃ Ph(4-Cl) Cl 4083. Me H Me Me OCH₂CF₃ 4084. Me H CF₃ Me

4085. Me H CF₃ Me H 4086. Me H CF₃ Me OCH₂CH₂OMe 4087. Me H CF₃ Me SMe 4088. Me H CF₃ Me OCH₂CH₂CH₂F 4089. Me H CF₃ Me OCH(CH₂F)₂ 4090. Me H CF₃ Me OCH₂CF₂CHF₂ 4091. Me H CF₃ Me OCH₂CF═CH₂ 4092. Me H CF₃ Me OCH(Me)CF₃ 4093. Me H CF₃ Me OCH(Me)CH₂F 4094. Me H OCH₂CF₃ Me CF₃ 4095. Me H OCH₂CF₃ Me CHF₂ 4096. Me H CHF₂ Me CHF₂ 4097. Me H CF₃ Me CHF₂ 4098. Me H Cl Me OCHF₂ 4099. Me H Br Me OCHF₂ 4100. Me H Br Me CF₃ 4101. H Me CF₃ Ph Cl 4102. H Me CF₃ ^(t)Bu Cl 4103. H Me CF₃ CHF₂ Cl 4104. H Me Cl CHF₂ CF₃ 4105. H Me CF₃ Me OMe 4106. H Me CF₃ Me CN 4107. H Me Cl Et Cl 4108. H Me CHF₂ Me Cl 4109. H Me Me Me Me 4110. H Me Me Me Cl 4111. H Me Cl Me Cl 4112. H Me CF₃ Me Cl 4113. H Me Cl Me CF₃ 4114. H Me CF₃ Me F 4115. H Me OMe Me CF₃ 4116. H Me CF₃ Me OEt 4117. H Me CF₃ Me OCHF₂ 4118. H Me OCHF₂ Me CF₃ 4119. H Me CF₃ Me OCH₂CHF₂ 4120. H Me CF₃ Me OCH₂CF₃ 4121. H Me CF₃ Me OCH₂CN 4122. H Me CF₃ Me SO₂Me 4123. H Me CF₃ Me SEt 4124. H Me CF₃ Me Me 4125. H Me CF₃ Me Et 4126. H Me CF₃ Et Cl 4127. H Me Cl Et CF₃ 4128. H Me CF₃ ^(i)Pr Cl 4129. H Me Cl ^(i)Pr CF₃ 4130. H Me CF₃ ^(t)Bu Cl 4131. H Me Cl ^(t)Bu CF₃ 4132. H Me CF₃ cPen Cl 4133. H Me Cl cPen CF₃ 4134. H Me CF₃ CH₂cPr Cl 4135. H Me Cl CH₂cPr CF₃ 4136. H Me CF₃ CH₂CH═CH₂ Cl 4137. H Me Cl CH₂CH═CH₂ CF₃ 4138. H Me CF₃ CHF₂ OMe 4139. H Me OMe CHF₂ CF₃ 4140. H Me CF₃ CH₂CF₃ Cl 4141. H Me Cl CH₂CF₃ CF₃ 4142. H Me CF₃ CH₂OMe Cl 4143. H Me Cl CH₂OMe CF₃ 4144. H Me CF₃ CH₂CN Cl 4145. H Me Me Ph Me 4146. H Me Me Ph Cl 4147. H Me Et Ph Cl 4148. H Me Pr Ph Cl 4149. H Me ^(i)Pr Ph Cl 4150. H Me CF₃ Ph Cl 4151. H Me CF₃ Ph Me 4152. H Me CF₃ Ph CF₃ 4153. H Me CF₃ Ph F 4154. H Me CF₃ Ph OMe 4155. H Me CF₃ Ph OEt 4156. H Me CF₃ Ph OCHF₂ 4157. H Me CF₃ Ph CN 4158. H Me CF₃ Ph(4-Cl) Cl 4159. H Me Me Me OCH₂CF₃ 4160. H Me CF₃ Me

4161. H Me CF₃ Me H 4162. H Me CF₃ Me OCH₂CH₂OMe 4163. H Me CF₃ Me SMe 4164. H Me CF₃ Me OCH₂CH₂CH₂F 4165. H Me CF₃ Me OCH(CH₂F)₂ 4166. H Me CF₃ Me OCH₂CF₂CHF₂ 4167. H Me CF₃ Me OCH₂CF═CH₂ 4168. H Me CF₃ Me OCH(Me)CF₃ 4169. H Me CF₃ Me OCH(Me)CH₂F 4170. H Me OCH₂CF₃ Me CF₃ 4171. H Me OCH₂CF₃ Me CHF₂ 4172. H Me CHF₂ Me CHF₂ 4173. H Me CF₃ Me CHF₂ 4174. H Me Cl Me OCHF₂ 4175. H Me Br Me OCHF₂ 4176. H Me Br Me CF₃ 4177. NO₂ H CF₃ Ph Cl 4178. NO₂ H CF₃ ^(t)Bu Cl 4179. NO₂ H CF₃ CHF₂ Cl 4180. NO₂ H Cl CHF₂ CF₃ 4181. NO₂ H CF₃ Me OMe 4182. NO₂ H CF₃ Me CN 4183. NO₂ H Cl Et Cl 4184. NO₂ H CHF₂ Me Cl 4185. NO₂ H Me Me Me 4186. NO₂ H Me Me Cl 4187. NO₂ H Cl Me Cl 4188. NO₂ H CF₃ Me Cl 4189. NO₂ H Cl Me CF₃ 4190. NO₂ H CF₃ Me F 4191. NO₂ H OMe Me CF₃ 4192. NO₂ H CF₃ Me OEt 4193. NO₂ H CF₃ Me OCHF₂ 4194. NO₂ H OCHF₂ Me CF₃ 4195. NO₂ H CF₃ Me OCH₂CHF₂ 4196. NO₂ H CF₃ Me OCH₂CF₃ 4197. NO₂ H CF₃ Me OCH₂CN 4198. NO₂ H CF₃ Me SO₂Me 4199. NO₂ H CF₃ Me SEt 4200. NO₂ H CF₃ Me Me 4201. NO₂ H CF₃ Me Et 4202. NO₂ H CF₃ Et Cl 4203. NO₂ H Cl Et CF₃ 4204. NO₂ H CF₃ ^(i)Pr Cl 4205. NO₂ H Cl ^(i)Pr CF₃ 4206. NO₂ H CF₃ ^(t)Bu Cl 4207. NO₂ H Cl ^(t)Bu CF₃ 4208. NO₂ H CF₃ cPen Cl 4209. NO₂ H Cl cPen CF₃ 4210. NO₂ H CF₃ CH₂cPr Cl 4211. NO₂ H Cl CH₂cPr CF₃ 4212. NO₂ H CF₃ CH₂CH═CH₂ Cl 4213. NO₂ H Cl CH₂CH═CH₂ CF₃ 4214. NO₂ H CF₃ CHF₂ OMe 4215. NO₂ H OMe CHF₂ CF₃ 4216. NO₂ H CF₃ CH₂CF₃ Cl 4217. NO₂ H Cl CH₂CF₃ CF₃ 4218. NO₂ H CF₃ CH₂OMe Cl 4219. NO₂ H Cl CH₂OMe CF₃ 4220. NO₂ H CF₃ CH₂CN Cl 4221. NO₂ H Me Ph Me 4222. NO₂ H Me Ph Cl 4223. NO₂ H Et Ph Cl 4224. NO₂ H Pr Ph Cl 4225. NO₂ H ^(i)Pr Ph Cl 4226. NO₂ H CF₃ Ph Cl 4227. NO₂ H CF₃ Ph Me 4228. NO₂ H CF₃ Ph CF₃ 4229. NO₂ H CF₃ Ph F 4230. NO₂ H CF₃ Ph OMe 4231. NO₂ H CF₃ Ph OEt 4232. NO₂ H CF₃ Ph OCHF₂ 4233. NO₂ H CF₃ Ph CN 4234. NO₂ H CF₃ Ph(4-Cl) Cl 4235. NO₂ H Me Me OCH₂CF₃ 4236. NO₂ H CF₃ Me

4237. NO₂ H CF₃ Me H 4238. NO₂ H CF₃ Me OCH₂CH₂OMe 4239. NO₂ H CF₃ Me SMe 4240. NO₂ H CF₃ Me OCH₂CH₂CH₂F 4241. NO₂ H CF₃ Me OCH(CH₂F)₂ 4242. NO₂ H CF₃ Me OCH₂CF₂CHF₂ 4243. NO₂ H CF₃ Me OCH₂CF═CH₂ 4244. NO₂ H CF₃ Me OCH(Me)CF₃ 4245. NO₂ H CF₃ Me OCH(Me)CH₂F 4246. NO₂ H OCH₂CF₃ Me CF₃ 4247. NO₂ H OCH₂CF₃ Me CHF₂ 4248. NO₂ H CHF₂ Me CHF₂ 4249. NO₂ H CF₃ Me CHF₂ 4250. NO₂ H Cl Me OCHF₂ 4251. NO₂ H Br Me OCHF₂ 4252. NO₂ H Br Me CF₃ 4253. CHF₂ H CF₃ Ph Cl 4254. CHF₂ H CF₃ ^(t)Bu Cl 4255. CHF₂ H CF₃ CHF₂ Cl 4256. CHF₂ H Cl CHF₂ CF₃ 4257. CHF₂ H CF₃ Me OMe 4258. CHF₂ H CF₃ Me CN 4259. CHF₂ H Cl Et Cl 4260. CHF₂ H CHF₂ Me Cl 4261. CHF₂ H Me Me Me 4262. CHF₂ H Me Me Cl 4263. CHF₂ H Cl Me Cl 4264. CHF₂ H CF₃ Me Cl 4265. CHF₂ H Cl Me CF₃ 4266. CHF₂ H CF₃ Me F 4267. CHF₂ H OMe Me CF₃ 4268. CHF₂ H CF₃ Me OEt 4269. CHF₂ H CF₃ Me OCHF₂ 4270. CHF₂ H OCHF₂ Me CF₃ 4271. CHF₂ H CF₃ Me OCH₂CHF₂ 4272. CHF₂ H CF₃ Me OCH₂CF₃ 4273. CHF₂ H CF₃ Me OCH₂CN 4274. CHF₂ H CF₃ Me SO₂Me 4275. CHF₂ H CF₃ Me SEt 4276. CHF₂ H CF₃ Me Me 4277. CHF₂ H CF₃ Me Et 4278. CHF₂ H CF₃ Et Cl 4279. CHF₂ H Cl Et CF₃ 4280. CHF₂ H CF₃ ^(i)Pr Cl 4281. CHF₂ H Cl ^(i)Pr CF₃ 4282. CHF₂ H CF₃ ^(t)Bu Cl 4283. CHF₂ H Cl ^(t)Bu CF₃ 4284. CHF₂ H CF₃ cPen Cl 4285. CHF₂ H Cl cPen CF₃ 4286. CHF₂ H CF₃ CH₂cPr Cl 4287. CHF₂ H Cl CH₂cPr CF₃ 4288. CHF₂ H CF₃ CH₂CH═CH₂ Cl 4289. CHF₂ H Cl CH₂CH═CH₂ CF₃ 4290. CHF₂ H CF₃ CHF₂ OMe 4291. CHF₂ H OMe CHF₂ CF₃ 4292. CHF₂ H CF₃ CH₂CF₃ Cl 4293. CHF₂ H Cl CH₂CF₃ CF₃ 4294. CHF₂ H CF₃ CH₂OMe Cl 4295. CHF₂ H Cl CH₂OMe CF₃ 4296. CHF₂ H CF₃ CH₂CN Cl 4297. CHF₂ H Me Ph Me 4298. CHF₂ H Me Ph Cl 4299. CHF₂ H Et Ph Cl 4300. CHF₂ H Pr Ph Cl 4301. CHF₂ H ^(i)Pr Ph Cl 4302. CHF₂ H CF₃ Ph Cl 4303. CHF₂ H CF₃ Ph Me 4304. CHF₂ H CF₃ Ph CF₃ 4305. CHF₂ H CF₃ Ph F 4306. CHF₂ H CF₃ Ph OMe 4307. CHF₂ H CF₃ Ph OEt 4308. CHF₂ H CF₃ Ph OCHF₂ 4309. CHF₂ H CF₃ Ph CN 4310. CHF₂ H CF₃ Ph(4-Cl) Cl 4311. CHF₂ H Me Me OCH₂CF₃ 4312. CHF₂ H CF₃ Me

4313. CHF₂ H CF₃ Me H 4314. CHF₂ H CF₃ Me OCH₂CH₂OMe 4315. CHF₂ H CF₃ Me SMe 4316. CHF₂ H CF₃ Me OCH₂CH₂CH₂F 4317. CHF₂ H CF₃ Me OCH(CH₂F)₂ 4318. CHF₂ H CF₃ Me OCH₂CF₂CHF₂ 4319. CHF₂ H CF₃ Me OCH₂CF═CH₂ 4320. CHF₂ H CF₃ Me OCH(Me)CF₃ 4321. CHF₂ H CF₃ Me OCH(Me)CH₂F 4322. CHF₂ H OCH₂CF₃ Me CF₃ 4323. CHF₂ H OCH₂CF₃ Me CHF₂ 4324. CHF₂ H CHF₂ Me CHF₂ 4325. CHF₂ H CF₃ Me CHF₂ 4326. CHF₂ H Cl Me OCHF₂ 4327. CHF₂ H Br Me OCHF₂ 4328. CHF₂ H Br Me CF₃ 4329. Cl Cl CF₃ Ph Cl 4330. Cl Cl CF₃ ^(t)Bu Cl 4331. Cl Cl CF₃ CHF₂ Cl 4332. Cl Cl Cl CHF₂ CF₃ 4333. Cl Cl CF₃ Me OMe 4334. Cl Cl CF₃ Me CN 4335. Cl Cl Cl Et Cl 4336. Cl Cl CHF₂ Me Cl 4337. Cl Cl Me Me Me 4338. Cl Cl Me Me Cl 4339. Cl Cl Cl Me Cl 4340. Cl Cl CF₃ Me Cl 4341. Cl Cl Cl Me CF₃ 4342. Cl Cl CF₃ Me F 4343. Cl Cl OMe Me CF₃ 4344. Cl Cl CF₃ Me OEt 4345. Cl Cl CF₃ Me OCHF₂ 4346. Cl Cl OCHF₂ Me CF₃ 4347. Cl Cl CF₃ Me OCH₂CHF₂ 4348. Cl Cl CF₃ Me OCH₂CF₃ 4349. Cl Cl CF₃ Me OCH₂CN 4350. Cl Cl CF₃ Me SO₂Me 4351. Cl Cl CF₃ Me SEt 4352. Cl Cl CF₃ Me Me 4353. Cl Cl CF₃ Me Et 4354. Cl Cl CF₃ Et Cl 4355. Cl Cl Cl Et CF₃ 4356. Cl Cl CF₃ ^(i)Pr Cl 4357. Cl Cl Cl ^(i)Pr CF₃ 4358. Cl Cl CF₃ ^(t)Bu Cl 4359. Cl Cl Cl ^(t)Bu CF₃ 4360. Cl Cl CF₃ cPen Cl 4361. Cl Cl Cl cPen CF₃ 4362. Cl Cl CF₃ CH₂cPr Cl 4363. Cl Cl Cl CH₂cPr CF₃ 4364. Cl Cl CF₃ CH₂CH═CH₂ Cl 4365. Cl Cl Cl CH₂CH═CH₂ CF₃ 4366. Cl Cl CF₃ CHF₂ OMe 4367. Cl Cl OMe CHF₂ CF₃ 4368. Cl Cl CF₃ CH₂CF₃ Cl 4369. Cl Cl Cl CH₂CF₃ CF₃ 4370. Cl Cl CF₃ CH₂OMe Cl 4371. Cl Cl Cl CH₂OMe CF₃ 4372. Cl Cl CF₃ CH₂CN Cl 4373. Cl Cl Me Ph Me 4374. Cl Cl Me Ph Cl 4375. Cl Cl Et Ph Cl 4376. Cl Cl Pr Ph Cl 4377. Cl Cl ^(i)Pr Ph Cl 4378. Cl Cl CF₃ Ph Cl 4379. Cl Cl CF₃ Ph Me 4380. Cl Cl CF₃ Ph CF₃ 4381. Cl Cl CF₃ Ph F 4382. Cl Cl CF₃ Ph OMe 4383. Cl Cl CF₃ Ph OEt 4384. Cl Cl CF₃ Ph OCHF₂ 4385. Cl Cl CF₃ Ph CN 4386. Cl Cl CF₃ Ph(4-Cl) Cl 4387. Cl Cl Me Me OCH₂CF₃ 4388. Cl Cl CF₃ Me

4389. Cl Cl CF₃ Me H 4390. Cl Cl CF₃ Me OCH₂CH₂OMe 4391. Cl Cl CF₃ Me SMe 4392. Cl Cl CF₃ Me OCH₂CH₂CH₂F 4393. Cl Cl CF₃ Me OCH(CH₂F)₂ 4394. Cl Cl CF₃ Me OCH₂CF₂CHF₂ 4395. Cl Cl CF₃ Me OCH₂CF═CH₂ 4396. Cl Cl CF₃ Me OCH(Me)CF₃ 4397. Cl Cl CF₃ Me OCH(Me)CH₂F 4398. Cl Cl OCH₂CF₃ Me CF₃ 4399. Cl Cl OCH₂CF₃ Me CHF₂ 4400. Cl Cl CHF₂ Me CHF₂ 4401. Cl Cl CF₃ Me CHF₂ 4402. Cl Cl Cl Me OCHF₂ 4403. Cl Cl Br Me OCHF₂ 4404. Cl Cl Br Me CF₃ 4405. Me Cl CF₃ Ph Cl 4406. Me Cl CF₃ ^(t)Bu Cl 4407. Me Cl CF₃ CHF₂ Cl 4408. Me Cl Cl CHF₂ CF₃ 4409. Me Cl CF₃ Me OMe 4410. Me Cl CF₃ Me CN 4411. Me Cl Cl Et Cl 4412. Me Cl CHF₂ Me Cl 4413. Me Cl Me Me Me 4414. Me Cl Me Me Cl 4415. Me Cl Cl Me Cl 4416. Me Cl CF₃ Me Cl 4417. Me Cl Cl Me CF₃ 4418. Me Cl CF₃ Me F 4419. Me Cl OMe Me CF₃ 4420. Me Cl CF₃ Me OEt 4421. Me Cl CF₃ Me OCHF₂ 4422. Me Cl OCHF₂ Me CF₃ 4423. Me Cl CF₃ Me OCH₂CHF₂ 4424. Me Cl CF₃ Me OCH₂CF₃ 4425. Me Cl CF₃ Me OCH₂CN 4426. Me Cl CF₃ Me SO₂Me 4427. Me Cl CF₃ Me SEt 4428. Me Cl CF₃ Me Me 4429. Me Cl CF₃ Me Et 4430. Me Cl CF₃ Et Cl 4431. Me Cl Cl Et CF₃ 4432. Me Cl CF₃ ^(i)Pr Cl 4433. Me Cl Cl ^(i)Pr CF₃ 4434. Me Cl CF₃ ^(t)Bu Cl 4435. Me Cl Cl ^(t)Bu CF₃ 4436. Me Cl CF₃ cPen Cl 4437. Me Cl Cl cPen CF₃ 4438. Me Cl CF₃ CH₂cPr Cl 4439. Me Cl Cl CH₂cPr CF₃ 4440. Me Cl CF₃ CH₂CH═CH₂ Cl 4441. Me Cl Cl CH₂CH═CH₂ CF₃ 4442. Me Cl CF₃ CHF₂ OMe 4443. Me Cl OMe CHF₂ CF₃ 4444. Me Cl CF₃ CH₂CF₃ Cl 4445. Me Cl Cl CH₂CF₃ CF₃ 4446. Me Cl CF₃ CH₂OMe Cl 4447. Me Cl Cl CH₂OMe CF₃ 4448. Me Cl CF₃ CH₂CN Cl 4449. Me Cl Me Ph Me 4450. Me Cl Me Ph Cl 4451. Me Cl Et Ph Cl 4452. Me Cl Pr Ph Cl 4453. Me Cl ^(i)Pr Ph Cl 4454. Me Cl CF₃ Ph Cl 4455. Me Cl CF₃ Ph Me 4456. Me Cl CF₃ Ph CF₃ 4457. Me Cl CF₃ Ph F 4458. Me Cl CF₃ Ph OMe 4459. Me Cl CF₃ Ph OEt 4460. Me Cl CF₃ Ph OCHF₂ 4461. Me Cl CF₃ Ph CN 4462. Me Cl CF₃ Ph(4-Cl) Cl 4463. Me Cl Me Me OCH₂CF₃ 4464. Me Cl CF₃ Me

4465. Me Cl CF₃ Me H 4466. Me Cl CF₃ Me OCH₂CH₂OMe 4467. Me Cl CF₃ Me SMe 4468. Me Cl CF₃ Me OCH₂CH₂CH₂F 4469. Me Cl CF₃ Me OCH(CH₂F)₂ 4470. Me Cl CF₃ Me OCH₂CF₂CHF₂ 4471. Me Cl CF₃ Me OCH₂CF═CH₂ 4472. Me Cl CF₃ Me OCH(Me)CF₃ 4473. Me Cl CF₃ Me OCH(Me)CH₂F 4474. Me Cl OCH₂CF₃ Me CF₃ 4475. Me Cl OCH₂CF₃ Me CHF₂ 4476. Me Cl CHF₂ Me CHF₂ 4477. Me Cl CF₃ Me CHF₂ 4478. Me Cl Cl Me OCHF₂ 4479. Me Cl Br Me OCHF₂ 4480. Me Cl Br Me CF₃ 4481. Cl Me CF₃ Ph Cl 4482. Cl Me CF₃ ^(t)Bu Cl 4483. Cl Me CF₃ CHF₂ Cl 4484. Cl Me Cl CHF₂ CF₃ 4485. Cl Me CF₃ Me OMe 4486. Cl Me CF₃ Me CN 4487. Cl Me Cl Et Cl 4488. Cl Me CHF₂ Me Cl 4489. Cl Me Me Me Me 4490. Cl Me Me Me Cl 4491. Cl Me Cl Me Cl 4492. Cl Me CF₃ Me Cl 4493. Cl Me Cl Me CF₃ 4494. Cl Me CF₃ Me F 4495. Cl Me OMe Me CF₃ 4496. Cl Me CF₃ Me OEt 4497. Cl Me CF₃ Me OCHF₂ 4498. Cl Me OCHF₂ Me CF₃ 4499. Cl Me CF₃ Me OCH₂CHF₂ 4500. Cl Me CF₃ Me OCH₂CF₃ 4501. Cl Me CF₃ Me OCH₂CN 4502. Cl Me CF₃ Me SO₂Me 4503. Cl Me CF₃ Me SEt 4504. Cl Me CF₃ Me Me 4505. Cl Me CF₃ Me Et 4506. Cl Me CF₃ Et Cl 4507. Cl Me Cl Et CF₃ 4508. Cl Me CF₃ ^(i)Pr Cl 4509. Cl Me Cl ^(i)Pr CF₃ 4510. Cl Me CF₃ ^(t)Bu Cl 4511. Cl Me Cl ^(t)Bu CF₃ 4512. Cl Me CF₃ cPen Cl 4513. Cl Me Cl cPen CF₃ 4514. Cl Me CF₃ CH₂cPr Cl 4515. Cl Me Cl CH₂cPr CF₃ 4516. Cl Me CF₃ CH₂CH═CH₂ Cl 4517. Cl Me Cl CH₂CH═CH₂ CF₃ 4518. Cl Me CF₃ CHF₂ OMe 4519. Cl Me OMe CHF₂ CF₃ 4520. Cl Me CF₃ CH₂CF₃ Cl 4521. Cl Me Cl CH₂CF₃ CF₃ 4522. Cl Me CF₃ CH₂OMe Cl 4523. Cl Me Cl CH₂OMe CF₃ 4524. Cl Me CF₃ CH₂CN Cl 4525. Cl Me Me Ph Me 4526. Cl Me Me Ph Cl 4527. Cl Me Et Ph Cl 4528. Cl Me Pr Ph Cl 4529. Cl Me ^(i)Pr Ph Cl 4530. Cl Me CF₃ Ph Cl 4531. Cl Me CF₃ Ph Me 4532. Cl Me CF₃ Ph CF₃ 4533. Cl Me CF₃ Ph F 4534. Cl Me CF₃ Ph OMe 4535. Cl Me CF₃ Ph OEt 4536. Cl Me CF₃ Ph OCHF₂ 4537. Cl Me CF₃ Ph CN 4538. Cl Me CF₃ Ph(4-Cl) Cl 4539. Cl Me Me Me OCH₂CF₃ 4540. Cl Me CF₃ Me

4541. Cl Me CF₃ Me H 4542. Cl Me CF₃ Me OCH₂CH₂OMe 4543. Cl Me CF₃ Me SMe 4544. Cl Me CF₃ Me OCH₂CH₂CH₂F 4545. Cl Me CF₃ Me OCH(CH₂F)₂ 4546. Cl Me CF₃ Me OCH₂CF₂CHF₂ 4547. Cl Me CF₃ Me OCH₂CF═CH₂ 4548. Cl Me CF₃ Me OCH(Me)CF₃ 4549. Cl Me CF₃ Me OCH(Me)CH₂F 4550. Cl Me OCH₂CF₃ Me CF₃ 4551. Cl Me OCH₂CF₃ Me CHF₂ 4552. Cl Me CHF₂ Me CHF₂ 4553. Cl Me CF₃ Me CHF₂ 4554. Cl Me Cl Me OCHF₂ 4555. Cl Me Br Me OCHF₂ 4556. Cl Me Br Me CF₃

In the tables below, retention times (R_(t), in minutes) of selected compounds of Tables 1-4 of chiral compounds were measured on chiral HPLC [Chiralcel® OD column (250×4.6 mm), temperature 25° C., flow rate 0.6 ml/min, mobile phase hexane/2-propanol 90:10].

TABLE 5 Compounds of the formula Ia-S (Ia-S)

Ex. Optical No. R¹¹ R¹² R¹ R² R³ R⁴ R⁵ rotation Physical data 185 Cl H Cl H H H Cl  *R_(t) = 20.123 min 259 Br H F H H H F  R_(t) = 17.053 min 270 Br H Cl H H H Cl [α]_(D) = +160° **R_(t) = 26.474 min *hexane/2-propanol 95:5 v/v. **hexane/2-propanol 97:3 v/v.

TABLE 6 Compounds of the formula Ia-R (Ia-R)

Ex. Optical No. R¹¹ R¹² R¹ R² R³ R⁴ R⁵ rotation Physical data 1375 Cl H Cl H H H Cl  *R_(t) = 22.213 min 1449 Br H F H H H F  R_(t) = 19.430 min 1460 Br H Cl H H H Cl [α]_(D) = −123° **R_(t) = 29.369 min *hexane/2-propanol 95:5 v/v. **hexane/2-propanol 97:3 v/v.

TABLE 7 Compounds of Tables 5 and 6 of the formula (Ia) (racemates) (Ia)

Ex. No. R¹¹ R¹² R¹ R² R³ R⁴ R⁵ 185/1375 Cl H Cl H H H Cl 259/1449 Br H F H H H F 270/1460 Br H Cl H H H Cl

NMR Data of the compounds of Tables 5+6 (CDCl₃, 400 MHz, δ in ppm):

NMR Compound 185/1375 (CDCl₃, 400 MHz):

-   4.74 (d, 1H, S(O)CH₂); 4.83 (d, 1H, S(O)CH₂); 7.23 (m, 1H, Ar); 7.33     (m, 2H, Ar); 7.67 (s, 1H, thiazolyl-H).

NMR Compound 259/1449 (CDCl₃, 400 MHz):

-   4.43 (d, 1H, S(O)CH₂); 4.52 (d, 1H, S(O)CH₂); 6.91 (m, 2H, Ar); 7.32     (m, 1H, Ar); 7.79 (s, 1H, thiazolyl-H).

NMR Compound 270/1460 (CDCl₃, 400 MHz):

-   4.74 (d, 1H, S(O)CH₂); 4.83 (d, 1H, S(O)CH₂); 7.24 (m, 1H, Ar); 7.34     (m, 2H, Ar); 7.77 (s, 1H, thiazolyl-H).

TABLE 8 Compounds of the formula Ib-S (Ib-S)

Ex. Optical No. R¹¹ R¹² R⁶ R⁷ R⁸ rotation Physical data 2555 Cl H CF₃ Me OCHF₂ [α]_(D) =   R_(t) = 10.081 min −69.6° 2632 Br H CF₃ Me Cl [α]_(D) =   R_(t) = 18.600 min −38.4° 2637 Br H CF₃ Me OCHF₂ [α]_(D) =  [α]_(D) = −66.6° −66.6°   R_(t) = 10.258 min 2719 I H CF₃ Me OCHF₂ [α]_(D) =   R_(t) = 12.775 min −59.8° 2640 Br H CF₃ Me OCH₂CF₃ [α]_(D) = ***R_(t) = 17.973 min −36.2° ***Column Chiralpak IC, Heptane 2-Propanol 90:10, 0.6 ml/min, 25° C.

TABLE 9 Compounds of the formula Ib-R (Ib-R)

Ex. Optical No. R¹¹ R¹² R⁶ R⁷ R⁸ rotation Physical data 3643 Cl H CF₃ Me OCHF₂ [α]_(D) =   R_(t) = 12.219 min +71.0° 3720 Br H CF₃ Me Cl [α]_(D) =   R_(t) = 22.652 min +40.3° 3725 Br H CF₃ Me OCHF₂ [α]_(D) =  [α]_(D) = +78.3° +78.3°   R_(t) = 12.557 min 3807 I H CF₃ Me OCHF₂ [α]_(D) =   R_(t) = 15.893 min +56.1° 3728 Br H CF₃ Me OCH₂CF₃ [α]_(D) = ***R_(t) = 16.446 min +68.4° ***Column Chiralpak IC, Heptane 2-Propanol 90:10, 0.6 ml/min, 25° C.

TABLE 10 Compounds of the formula (Ib) (racemates) (Ib)

Ex. No. R¹¹ R¹² R⁶ R⁷ R⁸ 2555/3643 Cl H CF₃ Me OCHF₂ 2632/3720 Br H CF₃ Me Cl 2637/3725 Br H CF₃ Me OCHF₂ 2719/3807 I H CF₃ Me OCHF₂ 2640/3728 Br H CF₃ Me OCH₂CF₃

NMR Data of the compounds of Tables 8+9 (CDCl₃, 400 MHz, δ in ppm):

NMR Compound 2555/3643 (CDCl₃, 400 MHz):

-   3.86 (s, 3H, NCH₃); 4.11 (d, 1H, S(O)CH₂); 4.37 (d, 1H, S(O)CH₂);     6.93 (dd, 1H, OCHF₂); 7.78 (s, 1H, thiazolyl-H).

NMR Compound 2632/3720 (CDCl₃, 400 MHz):

-   3.90 (s, 3H, NCH₃); 4.26 (d, 1H, S(O)CH₂); 4.35 (d, 1H, S(O)CH₂);     7.81 (s, 1H, thiazolyl-H).

NMR Compound 2637/3725 (CDCl₃, 400 MHz):

-   3.85 (s, 3H, NCH₃); 4.11 (d, 1H, S(O)CH₂); 4.37 (d, 1H, S(O)CH₂);     6.94 (dd, 1H, OCHF₂); 7.87 (s, 1H, thiazolyl-H).

NMR Compound 2719/3807 (CDCl₃, 400 MHz):

-   3.86 (s, 3H, NCH₃); 4.10 (d, 1H, S(O)CH₂); 4.36 (d, 1H, S(O)CH₂);     6.96 (dd, 1H, OCHF₂); 7.99 (s, 1H, thiazolyl-H).

NMR Compound 2640/3728 (CDCl₃, 400 MHz):

-   3.81 (s, 3H, NCH₃); 4.10 (d, 1H, S(O)CH₂); 4.35 (d, 1H, S(O)CH₂);     4.72 (qd, 1H, CH₂CF₃); 4.76 (qd, 1H, CH₂CF₃); 7.88 (s, 1H,     thiazolyl-H).

The retention times (R_(t), in minutes) of selected compounds of Tables 1-4 of chiral compounds were determined by analytical chiral HPLC [Chiralcel OD column (250×4.6 mm, particle size 5 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v or Chiralpak IC column, (250×4.6 mm, particle size 5 μm), temperature 25° C., flow rate 0.6 ml/min, hexane/2-propanol 90:10 v/v; if the solvent ratio is different, this is stated in the text.

NMR data were measured at 400 MHz and in the solvent CDCl₃. The chemical shift δ is stated in ppm (TMS reference).

B. FORMULATION EXAMPLES

-   a) A dust is obtained by mixing 10 parts by weight of a compound of     the formula (I) and 90 parts by weight of talc as inert substance     and comminuting the mixture in a hammer mill. -   b) A wettable powder which is readily dispersible in water is     obtained by mixing 25 parts by weight of a compound of the formula     (I), 64 parts by weight of kaolin-containing quartz as inert     substance, 10 parts by weight of potassium lignosulfonate and 1 part     by weight of sodium oleoylmethyltaurate as wetting agent and     dispersant, and grinding the mixture in a pinned-disk mill. -   c) A readily water-dispersible dispersion concentrate is obtained by     mixing 20 parts by weight of a compound of the formula (I) with 6     parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3     parts by weight of isotridecanol polyglycol ether (8 EO) and 71     parts by weight of paraffinic mineral oil (boiling range for example     about 255 to above 277° C.) and grinding the mixture in a ball mill     to a fineness of below 5 microns. -   d) An emulsifiable concentrate is obtained from 15 parts by weight     of a compound of the formula (I), 75 parts by weight of     cyclohexanone as solvent and 10 parts by weight of oxethylated     nonylphenol as emulsifier. -   e) Water-dispersible granules are obtained by mixing

75 parts by weight of a compound of the formula (I), 10 ″ of calcium lignosulfonate,  5 ″ of sodium lauryl sulfate,  3 ″ of polyvinyl alcohol and  7 ″ kaolin

-   -   grinding the mixture in a pinned-disk mill, and granulating the         powder in a fluidized bed by spraying on water as granulating         liquid.

-   f) Water-dispersible granules are also obtained by homogenizing and     precomminuting

25 parts by weight of a compound of the formula (I),  5 ″ of sodium 2,2′-dinaphthylmethane-6,6′-disulfonate,  2 ″ of sodium oleoylmethyltaurate,  1 part by weight of polyvinyl alcohol, 17 parts by weight calcium carbonate and 50 ″ of water

-   -   in a colloid mill, then grinding the mixture in a bead mill, and         atomizing and drying the resulting suspension in a spray tower,         using a single-fluid nozzle.

C. BIOLOGICAL EXAMPLES

1. Pre-Emergence Herbicidal Effect And Crop Plant Compatibility

Seeds of monocotyledonous or dicotyledonous weed plants or crop plants are placed in sandy loam in wood-fiber pots and covered with soil. The compounds according to the invention, formulated in the form of wettable powders (WP), are then applied as aqueous suspension at a water application rate of 600 l/ha (converted) with the addition of 0.2% of wetting agent to the surface of the covering soil.

After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the test plants. After about 3 weeks, the effect of the preparations is scored visually in comparison with untreated controls (herbicidal effect in percent (%): 100% activity=the plants have died, 0% activity=like control plants).

As shown by the results, the compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of weed grasses and broad-leaved weeds. The compounds Nos. 185, 259, 270, 2555, 2632, 2637, 2719, 1375, 1449, 1460, 3643, 3720, 3725, 2640, 3728 and other compounds from Tables 1-4, for example, have very good herbicidal activity against harmful plants such as, for example, Avena fatua, Stellaria media, Echinochloa crus galli, Lolium multiflorum, Setaria viridis, Abutilon theophrasti, Amaranthus retroflexus, Viola tricolor, Veronica persica and Alopecurus myosuroides when applied by the pre-emergence method at an application rate of 0.32 kg and less of active substance per hectare.

In addition, some substances also spare monocotyledonous and dicotyledonous crops such as wheat and oilseed rape. Some of the compounds according to the invention have high selectivity and are therefore suitable for controlling unwanted vegetation in agricultural crops by the pre-emergence method.

The following results were achieved with the compounds of the formula (Ia) by the pre-emergence method:

according to the Compound invention TRZAS ECHCG LOLMU SETVI VIOTR 185 80 g of 10 100 90 100 70 (S config.) active com- pound/ha 20 g of 0 90 70 70 60 active com- pound/ha Racemate 80 g of 50 90 40 80 0 of 185 active com- (S config.) pound/ha and 1375 20 g of 50 50 40 30 0 (R config.) active com- pound/ha 1375 80 g of 0 80 60 20 80 (R config.) active com- pound/ha 20 g of 0 0 0 0 60 active com- pound/ha

From the above table, it can be deduced that the (S) and (R) stereoisomers of the compounds of the formula (Ia) according to the invention have better herbicidal action against the weed grasses examined than the racemic mixture. At the same time, the crop plant compatibility of the (S) and (R) stereoisomers in wheat is surprisingly high. In particular the simultaneous effect of an enhanced activity against weed grasses and better compatibility with specific crops of the individual stereoisomers was unexpected based on the prior art.

The following results were achieved with the compounds of the formula (Ib) by the pre-emergence method:

according to the Compound invention BRSNW ALOMY LOLMU SETVI 2637 80 g of 0 90 100 90 (S config.) active com- pound/ha 20 g of 0 60 10 80 active com- pound/ha Racemate 80 g of 0 90 80 80 of 2637 active com- (S config.) pound/ha and 3725 20 g of 0 30 0 0 (R config.) active com- pound/ha 3725 80 g of 0 20 0 0 (R config.) active com- pound/ha 20 g of 0 0 0 0 active com- pound/ha

From the above table, it can be deduced that the (S) stereoisomers of the compounds of the formula (I) according to the invention have better herbicidal action against the weed grasses examined than the racemic mixture. At the same time, the crop plant compatibility of the (S) stereoisomers in oilseed rape is surprisingly high, i.e. at increased activity a higher selectivity is achieved, too.

The following results were achieved with the compounds of the formula (Ib) by the post-emergence method:

according to the Compound invention ZEAMX AVEFA LOLMU SETVI POLCO STEME 2640 80 g of 0 90 100 100 100 90 (S config.) active com- pound/ha 20 g of 0 20 60 100 20 10 active com- pound/ha Racemate 80 g of 0 70 80 100 80 20 of 2640 active com- (S config.) pound/ha and 3728 20 g of 0 20 0 20 0 10 (R config.) active com- pound/ha 3728 80 g of 0 10 0 10 10 10 (R config.) active com- pound/ha 20 g of 0 0 0 10 — 0 active com- pound/ha

From the above table, it can be deduced that the (S) stereoisomers of the compounds of the formula (I) according to the invention have better herbicidal action against the weed grasses examined than the racemic mixture. At the same time, the crop plant compatibility of the (S) stereoisomers in oilseed rape is surprisingly high, i.e. at increased activity a higher selectivity is achieved, too.

Abbreviations

-   ZEAMX: Zea mays (corn) -   TRZAS: Triticum aestivum (summer wheat) -   ALOMY: Alopecurus myosuroides (black-grass) -   LOLMU: Lolium multiflorum (Italian ryegrass) -   SETVI: Setaria viridis (green foxtail) -   BRSNW: Brassica napus (winter rape) -   VIOTR: Viola tricolor (wild pansy) -   ECHCG: Echinochloa crus-galli (barnyard grass) -   AVEFA: Avena fatua -   POLCO: Polygunum convolvulus -   STEME: Stellaria media     2. Post-Emergence Herbicidal Effect and Crop Plant Compatibility

Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in wood fibre pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated at the one-leaf stage. The compounds according to the invention, formulated in the form of wettable powders (WP), are then applied as aqueous suspension at a water application rate of 600 l/ha (converted) with the addition of 0.2% of wetting agent to the green parts of the plants. After the test plants have been kept in the greenhouse under optimum growth conditions for about 3 weeks, the activity of the preparations is rated visually in comparison to untreated controls (herbicidal activity in percent (%): 100% activity=the plants have died, 0% activity=like control plants).

As shown by the results, the compounds according to the invention have good herbicidal post-emergence activity against a plurality of weed grasses and broad-leaved weeds. The compounds Nos. 185, 259, 270, 2555, 2632, 2637, 2719, 1375, 1449, 3643, 3720, 3725, 2640, 3728 and other compounds from Tables 1-4, for example, have very good herbicidal activity against harmful plants such as, for example, Avena fatua, Echinochloa crus galli, Lolium multiflorum, Setaria viridis and Alopecurus myosuroides when applied by the post-emergence method at an application rate of 0.32 kg and less of active substance per hectare.

In addition, some substances also spare graminaceous and dicotyledonous crops such as corn and oilseed rape. Some of the compounds according to the invention have high selectivity and are therefore suitable for controlling unwanted vegetation in agricultural crops by the post-emergence method. 

The invention claimed is:
 1. An optically active compound of formula (I) in the (S) configuration and/or an agrochemically acceptable salt and/or an agrochemically acceptable quaternized nitrogen derivative thereof

wherein Y is

and the substituents R¹ to R⁵ are each independently of one another selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, C(O)OH, formyl, (C₁-C₆)-alkyl, (C₁-C₆)-haloalkyl, (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-haloalkylcarbonyl, (C₁-C₆)-alkylcarbonyloxy, (C₁-C₆)-haloalkylcarbonyloxy, (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-alkyl, (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-alkyl, (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-haloalkyl, (C₁-C₆)-haloalkylcarbonyl-(C₁-C₄)-haloalkyl, (C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₁-C₆)-alkoxycarbonyl, (C₁-C₆)-haloalkoxycarbonyl, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkoxycarbonyl-(C₁-C₆)-haloalkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-haloalkenyl, (C₂-C₆)-alkenylcarbonyl, (C₂-C₆)-haloalkenylcarbonyl, (C₂-C₆)-alkenyloxy, (C₂-C₆)-haloalkenyloxy, (C₂-C₆)-alkenyloxycarbonyl, (C₂-C₆)-haloalkenyloxycarbonyl, (C₂-C₆)-alkynyl, (C₂-C₆)-haloalkynyl, (C₂-C₆)-alkynylcarbonyl, (C₂-C₆)-haloalkynylcarbonyl, (C₂-C₆)-alkynyloxy, (C₂-C₆)-haloalkynyloxy, (C₂-C₆)-alkynyloxycarbonyl, (C₂-C₆)-haloalkynyloxycarbonyl, (C₁-C₆)-alkylthiocarbonyl, (C₁-C₆)-haloalkylthiocarbonyl, (C ₁-C₆)-alkylthiocarbonyloxy, (C₁-C₆)-haloalkylthiocarbonyloxy, (C₁-C₆)-alkylthio-(C₁-C₆)-alkoxy, (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyl, (C₁-C₆)-alkylthio-(C₁-C₆)-alkylcarbonyloxy, (C₆-C₁₄)-aryl, (C₆-C₁₄)-aryloxy, (C₆-C₁₄)-arylcarbonyl, (C₆-C₁₄)-aryloxycarbonyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxy, (C₆-C₁₄)-aryloxy-(C₁-C₆)-alkyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl-carbonyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl-carbonyloxy, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxycarbonyloxy, (C₁-C₆)-alkylsulfonyl, (C₁-C₆)-alkylthio, (C₁-C₆)-alkylsulfinyl, (C₁-C₆)-halo-alkylsulfonyl, (C₁-C₆)-haloalkylthio, (C₁-C₆)-haloalkylsulfinyl, (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkylthio-(C₁-C₆)-alkyl, (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkylthio-(C₁-C₆)-alkyl, (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-alkylthio-(C₁-C₆)-haloalkyl, (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkylsulfonyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkylthio-(C₁-C₆)-haloalkyl, (C₁-C₆)-haloalkylsulfinyl-(C₁-C₆)-haloalkyl, (C₁-C₆)-alkylsulfonyloxy, (C₁-C₆)-haloalkylsulfonyloxy, (C₄-C₁₄)-arylsulfonyl, (C₆-C₁₄)-arylthio, (C₆-C₁₄)-arylsulfinyl, mono-((C₁-C₆)-alkyl)-amino, mono-((C₁-C₆)-haloalkyl)-amino, di-((C₁-C₆)-alkyl)-amino, di-((C₁-C₆)-haloalkyl)-amino, ((C₁-C₆)-alkyl-(C₁-C₆)-haloalkyl)-amino, N—((C₁-C₆)-alkanoyl)-amino, N—((C₁-C₆)-haloalkanoyl)-amino, aminocarbonyl-(C₁-C₆)-alkyl, mono-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl, di-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₆)-alkyl, mono-((C₁-C₆)-alkyl)-aminocarbonyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkoxy, (C₁-C₆)-alkoxy-carbonyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkyl, (C₃-C₈)-cycloalkoxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxy, (C₃-C₈)-cycloalkylcarbonyl, (C₃-C₈)-cycloalkoxycarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkoxycarbonyl, (C₃-C₈)-cycloalkylcarbonyloxy, (C₃-C₈)-cycloalkoxycarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkylcarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-haloalkylcarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxycarbonyloxy, (C₃-C₈)-cycloalkyl-(C₁-C₆) -haloalkoxycarbonyloxy, (C₃-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkenyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxy, (C₃-C₈)-cycloalkenylcarbonyl, (C₃-C₈)-cycloalkenyloxycarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyl, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyl, (C₃-C₈)-cycloalkenylcarbonyloxy, (C₃-C₈)-cycloalkenyloxycarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkylcarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkylcarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-alkoxycarbonyloxy, (C₃-C₈)-cycloalkenyl-(C₁-C₆)-haloalkoxycarbonyloxy, (C₃-C₈)-cycloalkylthio, (C₃-C₈)-alkenylthio, (C₃-C₈)-cycloalkenylthio, (C₃-C₆)-alkynylthio, hydroxy-(C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkyl, 3-oxetanyloxy, and C(O)NR⁹R¹⁰ where R⁹ and R¹⁰ independently of one another are hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰together form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups, where the R¹ to R⁵ substituents may, if appropriate, be attached cyclically to one another, provided they are ortho to one another and/or two of the R¹ to R⁵ substituents ortho to one another together form a (C₁-C₆)-alkylene group which may contain one or more oxygen and/or sulfur atoms, where the (C₁-C₆)-alkylene group may be mono- or polysubstituted by halogen and the halogen substituents in question may be identical or different; where the radicals R¹ to R⁵ mentioned above may be mono- or polysubstituted independently of one another by at least one radicals selected from the group consisting of (C₁-C₆)-alkyl, (C₁-C₆)-alkoxy, nitro, cyano, (C₁-C₃)-cycloalkyl, (C₁-C₆)-haloalkoxy, and (C₁-C₆)-alkylthio and halogen, where the radicals mentioned may optionally be cyclically attached to one another, provided they are ortho to each other; and the substituents R¹¹ and R¹², in each case independently of one another, are selected from the group consisting of hydrogen, halogen, nitro, cyano, formyl, C(O)OH, hydroxyl, amino, (C₁-C₆)-alkyl, (C₁-C₆)-alkylcarbonyl, (C₁-C₆)-alkylcarbonyl-(C₁-C₄)-alkyl, (C₁-C₆)-alkylcarbonyloxy, (C₁-C₆)-alkoxy, (C₁-C₆)-alkoxycarbonyl, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkyl, (C₁-C₆)-alkoxy-(C₁-C₆)-alkoxy, (C₁-C₆)-alkoxycarbonyl-(C₁-C₆)-alkoxy, (C₂-C₆)-alkenyl, (C₂-C₆)-alkenyloxy, (C₂-C₆)-alkynyl, (C₂-C₆)-alkynyloxy, (C₁-C₆)-alkylthio, (C₁-C₆)-alkylsulfinyl, (C₁-C₆)-alkylsulfonyl, (C₁-C₆)-alkylsulfonyloxy, (C₁-C₆)-alkylsulfonyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkylsulfinyl-(C₁-C₆)-alkyl, (C₁-C₆)-alkylthio-(C₁-C₆)-alkyl, (C₁-C₆)-alkylthio-(C₁-C₆)-alkoxy, mono-((C₁-C₆)-alkyl)-amino, di-((C₁-C₆)-alkyl)-amino, N—((C₁-C₆)-alkanoyl)-amino, aminocarbonyl-(C₁-C₆)-alkyl, mono-((C₁-C₆)-alkyl)-aminocarbonyl, di-((C₁-C₆)-alkyl)-aminocarbonyl, mono-((C₁-C₆)-alkyl)-aminosulfonyl, di-((C₁-C₆)-alkyl)-aminosulfonyl, (C₃-C₈)-cycloalkyl, (C₃-C₈)-cycloalkoxy, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkyl, (C₃-C₈)-cycloalkyl-(C₁-C₆)-alkoxy, (C₃-C₈)-cycloalkylcarbonyl, (C₃-C₈)-cycloalkoxycarbonyl, (C₃-C₈)-cycloalkenyl, (C₃-C₈)-cycloalkenyloxy, (C₃-C₈)-cycloalkylthio, (C₃-C₈)-cycloalkylsulfinyl, (C₃-C₈)-cycloalkylsulfonyl, (C₃-C₈)-cycloalkylsulfonyloxy, cyano-(C₁-C₆)-alkoxy, cyano-(C₁-C₆)-alkyl, (C₆-C₁₄)-aryl, (C₆-C₁₄)-aryloxy, (C₆-C₁₄)-aryl-(C₁-C₆)-alkyl, (C₆-C₁₄)-aryl-(C₁-C₆)-alkoxy, (C₆-C₁₄)-aryloxy-(C₁-C₆)-alkyl, —CONH—SO₂—(C₁-C₆)-alkyl, —NHCHO, —NHCO—(C₁-C₆)-alkyl, —NHCO₂—(C₁-C₆)-alkyl, —NHCONH—(C₁-C₆)-alkyl, —NHSO₂—(C₁-C₆)-alkyl, —OCONH—(C₁-C₆)-alkyl, (C₁-C₆)-alkylaminosulfonyl-(C₁-C₂)-alkyl, di-(C₁-C₆)-alkylaminosulfonyl-(C₁-C₂)-alkyl, —C(O)NHR⁹, and —C(O)NR⁹R¹⁰ where R⁹ and R¹⁰ independently of one another are hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups, where the radicals R¹¹ and R¹² mentioned above may be mono- or polysubstituted independently of one another by radicals selected from the group consisting of halogen and (C₁-C₆)-alkyl.
 2. The compound of the formula (I) as claimed in claim 1 wherein Y is

and the substituents R¹ to R⁵ independently of one another are selected from the group consisting of hydrogen, hydroxyl, halogen, cyano, nitro, amino, C(O)OH, (C₁-C₄)-alkyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkoxy-(C₁-C₂)-alkyl, (C₁-C₃)-alkylcarbonyl, (C₁-C₃)-alkylcarbonyloxy, (C₁-C₄)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl, (C₃-C₆)-cycloalkyl-(C₁-C₂)-alkoxy, (C₃-C₆)-cycloalkoxy, (C₁-C₄)-alkoxycarbonyl-(C₁-C₂)-alkoxy, (C₃-C₄)-alkenyloxy, (C₃-C₄)-alkynyloxy, (C₁-C₄)-alkylthio, (C₁-C₄)-haloalkylthio, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-haloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-haloalkylsulfonyl, (C₁-C₄)-alkylsulfonyloxy, di-(C₁-C₄)-alkylamino, C₆-aryl-(C₁-C₄)-alkyl, (C₃-C₄)-alkenyloxycarbonyl, (C₂-C₄)-alkynyloxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxycarbonyl, C₆-aryl-(C₁-C₄)-alkoxy, formyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, phenyl, and —C(O)NR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another are selected from the group consisting of hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, and (C₁-C₆)-haloalkyl, or where R⁹ and R¹⁰ together form a (C₁-C₆)-alkylene group which may contain one oxygen or sulfur atom or one or two amino or (C₁-C₆)-alkylamino groups.
 3. The compound of the formula (I) as claimed in claim 1 wherein R¹¹ and R¹² independently of one another are selected from the group consisting of hydrogen, halogen, nitro, cyano, carboxyl, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, (C₃-C₆)-cycloalkoxy, (C₁-C₆)-alkoxy, (C₁-C₆)-alkylcarbonyl, (C₃-C₆)-cycloalkylcarbonyl, (C₁-C₆)-alkoxycarbonyl, (C₃-C₆)-cycloalkoxycarbonyl, mono-((C₁-C₄)-alkyl)-aminocarbonyl, di-((C₁-C₄)-alkyl)-aminocarbonyl, mono-((C₁-C₄)-alkyl)-aminosulfonyl, di-((C₁-C₄)-alkyl)-aminosulfonyl, (C₁-C₄)-alkylthio, (C₃-C₆)-cycloalkylthio, (C₁-C₄)-alkylsulfinyl, (C₃-C₆)-cycloalkylsulfinyl, (C₁-C₄)-alkylsulfonyl, (C₃-C₆)-cycloalkylsulfonyl, (C₁-C₄)-alkylsulfonyloxy, (C₃-C₆)-cycloalkylsulfonyloxy, (C₂-C₃)-alkenyl, (C₂-C₃)-alkynyl, (C₂-C₃)-alkenyloxy, (C₂-C₃)-alkynyloxy, —NHCO—(C₁-C₃)-alkyl, —NHCO₂—(C₁-C₃)-alkyl, —NHCONH—(C₁-C₃)-alkyl, —NHSO₂—(C₁-C₃)-alkyl, —OCONH—(C₁-C₃)-alkyl, —CONHR⁹, and —CONR⁹R¹⁰, where R⁹ and R¹⁰ independently of one another are hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, or (C₁-C₆)-haloalkyl, where the radicals R¹¹ and R¹² mentioned above may be mono- or polysubstituted independently of one another by radicals selected from the group consisting of halogen and (C₁-C₆)-alkyl.
 4. The compound of the formula (I) as claimed in claim 1 wherein R¹¹ and R¹² independently of one another are selected from the group consisting of H, F, Cl, Br, I, Me, CHF₂ and CF₃.
 5. The compound of the formula (I) as claimed in claims 1 wherein R¹¹ and R¹² independently of one another are selected from the group consisting of F, Cl, Br and I.
 6. The compound according to claim 1 in which Y is

and the radicals R¹ to R⁵ and R¹¹ and R¹² have the meanings according to claim 1, except for the compounds 2-(benzylsulfinyl)-1,3-thiazole, 2-(benzylsulfinyl)-5-(chloromethyl)-1,3-thiazole, 5-(chloromethyl)-2-(4-methylbenzyl)sulfinyl-1,3-thiazole, 5-(chloromethyl)-2-(4-methoxybenzyl)sulfinyl-1,3-thiazole, 2-(4-chlorobenzyl)sulfinyl-5-(chloromethyl)-1,3-thiazole, 5-(chloromethyl)-2-(4-nitrobenzyl)sulfinyl-1,3-thiazole, 5-(bromomethyl)-2-(4-nitrobenzyl)sulfinyl-1,3-thiazole, 5-(bromomethyl)-2-(4-chlorobenzyl)sulfinyl-1,3-thiazole, 5-(bromomethyl)-2-(4-methoxybenzyl)sulfinyl-1,3-thiazole, 5-(bromomethyl)-2-(4-methylbenzyl)sulfinyl-1,3-thiazole and 2-(benzylsulfinyl)-5-(bromomethyl)-1,3-thiazole.
 7. A process for preparing a compound of the formula (I) as claimed in claim 1, which comprises oxidizing a thioether of the formula (II)

with one equivalent of an oxidizing agent to give a sulfoxide of the formula (I)


8. The process as claimed in claim 7 wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, sodium metaperiodate, organic peroxides and organic peracids.
 9. A composition comprising at least one compound of the formula (I) as claimed in claim
 1. 10. The composition as claimed in claim 9 wherein the composition comprises at least one further active compound selected from the group consisting of at least one further herbicide and at least one safener.
 11. A plant growth regulator comprising a compound of the formula (I) as claimed in claim
 1. 12. A plant growth regulator comprising a composition as claimed in claim
 9. 13. A method for controlling plants in specific plant crops comprising applying plant protection regulator of claim 9 to said crops.
 14. The compound of the formula (I) as claimed in claim 1 wherein R¹, R⁵ and R¹¹ are halogen and R², R³, R⁴ and R¹² are hydrogen, and Y is phenyl. 